WO1986004694A1 - Silver halide photographic photo-sensitive material - Google Patents

Abstract

A silver halide photographic photo-sensitive material, in which a highly immobile novel arylidenebis type of dye which selectively dyes a specific layer and does not diffuse into other layers is incorporated in a hydrophilic colloidal layer. The dye used in this photo-sensitive material can be easily removed upon photographic processing, and does not adversely affect photographic properties, particularly spectral sensitization, of the photographic emulsions.

Description

 Handbook Silver halide photographic light-sensitive material

 The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid colored by a novel dye.

Background engineer

 In a silver octalogen photographic light-sensitive material, photographic emulsions and other hydrophilic colloids are often colored in order to absorb light in a specific wavelength range.

 When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion, a colored slaughter is usually provided farther from the support than the photographic emulsion I. Such a coloring 曆 is called a filter 曆. If there is more than one photographic emulsion layer, one filter layer may be located between them.

The light scattered during or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion and the support or at the surface of the photosensitive material on the side opposite to the photographic material and re-enters the photographic material. To prevent blurring of the image, that is, halation, a coloring layer called anti-halation is provided between the photographic emulsion layer and the support or on the opposite side of the support from the photographic emulsion. Is done. If there are multiple photographic emulsion layers, an anti-halation slaughter is placed between those layers There are things.

 In order to prevent the loss of image sharpness due to the scattering of light in the photographic agent (this phenomenon is commonly called an illumination), the photographic agent is also colored.

 These hydrophilic colloid layers to be colored usually contain a dye. This dye must satisfy the following conditions.

 (1) Have appropriate spectral absorption according to the purpose of use.

 (2) Photochemically inert. That is, it must not adversely affect the performance of silver halide photographic emulsions in a chemical sense, such as loss of sensitivity, latent image regression, or capri.

 (3) No decoloration during the photographic processing or elution in the processing solution or washing water, leaving no harmful coloring on the processed photographic material.

 (4) Do not spread from the dyed layer to other slaughter.

 (5) It has excellent stability over time in a solution or photographic material and does not discolor.

As a supplement to (4) above, if the colored slaughter is a single-layer filter, or if the slaughter is anti-halation on the same side as the photographic emulsion そ れ ら, the slaughter should be selected. It is often necessary to ensure that the colored layer is substantially colored and that the other layers are substantially free of color. This is because otherwise, it not only has a detrimental spectral effect on the other 曆, but also diminishes its effect as a filter 曆 or as an anti-halation slaughter. Thus, adding the dye When the 曆 and the other hydrophilic colloid layer come into contact with each other in a wet state, the — part of the dye often diffuses from the former to the latter. Such diffusion of the dye largely depends on the chemical structure of the dye used.

 More efforts have been made to find dyes that meet these conditions. For example, UK Patent No. 506,385, U.S. Patent Nos. 3,247,127, 2,533,472, 3,379,533, United Kingdom Oxonol dyes as described in Patent Nos. 1, 278, 621; hemioxonol dyes represented by dyes described in British Patent No. 5,846,09; U.S. Pat. Styryl dyes represented by the dyes described in No. 98,733, merocyanine dyes such as the dyes described in U.S. Pat.No. 2,493,747, U.S. Pat.No. 2,843,486 And cyanine dyes typified by the dyes described in (1).

 Most of the dyes that are decolorized in the course of photographic emulsions are dyes that are late-colored depending on the phosphite (or acid phosphite) contained in the processing solution or the alkaline conditions. For example, as described in British Patent No. 506,385.

 In U.S. Pat. Nos. 3,002,837 and 3,389,994, bis-type dyes having a vilazolone ring structure have been started.

However, the dyes described in the conventional literature each have advantages and disadvantages, and when used in a silver halide photographic light-sensitive material, it is difficult to say that all of the above conditions (1) to (5) are satisfied. Silver halide photographic exposure There is a need for the development of high performance dyes that can be used in materials.

Disclosure of the invention

 The first object of the invention is to obtain a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel dye which selectively dyes a specific color and does not diffuse to other layers. is there.

 The second object of the invention is to provide a silver halide photograph having a hydrophilic colloid II containing a novel dye which is colored in photographic processing and does not adversely affect the photographic properties of the photographic emulsion, especially the spectral sensitization. That is, to obtain a photosensitive material.

 It has been found that the above object can be attained by a silver halide photographic material having at least one kind of compound represented by the following general formulas (I) to (¾).

 That is, the present invention provides a silver halide photographic material comprising at least one compound represented by the following general formulas (I) to (71).

 General formula (I)

Z ₂

—General formula (Π)

General formula (ΙΠ)

-General formula (IV)

General formula (V)

—Ft expression ()

(Wherein, X ₂ , X 3, and X may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group, Represents a sulfamoyl group or an alkoxycarbonyl group.

RX, R ₂ , R ₃ , and R ₄ may be the same or different and include a chromium atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, and an acyl group. And a sulfonyl group. In the general formulas (m) to (VI), R ₂ or R ₃ or R ₄ may form a 5- or 6-membered group.

Z 1, Z 2, Z ₃ and Z 4 may be the same or different and represent an electron-withdrawing group. Also, and Z ₂ or Z ₃ and ζ ₄ may be linked to form a ring. Zeta _5, Zeta 6 is rather good be the same or different, represents an atomic group for forming a瑗, zeta _7, Zeta ₈ represents a good electron-withdrawing group be made the same or different.

Upsilon 1, Upsilon 2 represents a divalent Ken'yui group, Υ _3, Υ 4 represents a divalent linking group having a good electron-withdrawing be made the same or different.

 L represents an unsubstituted or substituted methine tomb. m and n are 0 or 1. )

 The dye compounds represented by the general formulas (I) to (VI) will be described in more detail.

In the formula,, X ₂ , X 3, and X 4 may be the same or different, and include a hydrogen atom, a halogen atom, an alkyl group having preferably 1 to 6 carbon atoms, and an alkyl group having preferably 1 to 6 carbon atoms. Alkoxy group, hydroxy group, carboxyl group, substituted amino group (preferably having 1 to 6 carbon atoms Amino group substituted by an acyl group derived from an aromatic carboxylic acid or sulfonic acid, an alkylamino group having preferably 1 to 6 carbon atoms, and a dialkylamino having 1 to 6 carbon atoms And the like, a carbon number of preferably 2 to 7; a carbamoyl group; a carbon number of preferably 1 to 6; a sulfamoyl group; or a carbon number of 2 to 6 alkoxycarbonyl group.

R 1, R ₂ , R ₃ , and-may be the same or different from each other, and include a hydrogen atom, an unsubstituted or fully substituted alkyl group having 1 to 8 carbon atoms (substituents such as rho and , Hydroxy, cyano, alkoxy, acyl, acyloxy, acylamino, carbamoyl, alkylamino, dialkylamino, carboxyl, alkoxycarbonyl, sulfonyl, sulfonylamino , Sulfamoyl tombs, sulfo groups, aryl groups, etc.), alkenyl groups having preferably 2 to 6 carbon atoms, unsubstituted or substituted aryls ≤ {preferably unsubstituted or substituted phenyl groups (as substituents) Represents a halogen atom, a cyano group, a sulfo grave, a hydroxy group, a carboxyl group, an alkoxy group, an alkyl group, a nitro group, etc.)} Or an alkylsulfonyl group having preferably 1 to 6 carbon atoms, or an unsubstituted or substituted arylsulfonyl group {preferably an unsubstituted or substituted phenyl group (halogen as a substituent) Atom, cyano group, sulfo group, hydroxy group, alkoxy group, alkyl group, etc.)}.

Z _t , Z ₂ , Z 3, Z, may be the same or different, and preferably have 2 to 13 carbon atoms, preferably 2 to 13 carbon atoms, and preferably 2 to 3 carbon atoms. 13 unsubstituted or substituted alkoxycarbonyl group having preferably 13 to 10 carbon atoms, preferably 2 to 10 carbon atoms (substituents include a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an acyl group, an acylamino Group, alkylamino group, dialkylamino group, carbonyl group, alkoxycarbonyl group, sulfonyl group, sulfonylamino group, sulfo group, aryl group, etc., unsubstituted or substituted aryloxycarbonyl group (substituted halogen Atom, alkyl group, alkoxy group, nitro group, hydroxy group, carboxy group, sulfo group, cyano group, unsubstituted or substituted amino group (alkyl group, acyl group, alkylsulfonyl group, etc. for the allocation group) , An alkoxy group, a luponyl group, etc.} The carbon number is preferably 1 to 12 Sulfo group, preferably carbon atoms 1-1 2 Surupuamoiru group, an electron withdrawing group such as Shiano group. Further, Zeta iota and Z ₂ are coupled ring (eg, Birazoron ring, Birazorotoriazo one Ruzo, virazoloimidazoyl, oxindole ring, oximidazoviridine ring, isoxazolone, barbituric acid, dioxytetrahydroviridine, indandione ring, etc. Z The same is true for 3 and Z 4.

Z ₅ and Z 6 may be the same or different and may be selected from the group consisting of 瓖 (for example, virazolone 瓖, virazolotriazol 一, vilazoloimidazole 瓖, oxindole ring, oxyimidazoviridine ring, isoxazolone ロ ン, barbituric acid Ring, dioxytetrahydroviridine ring, indandione ring, etc.). Z ₇ and Z β may be the same or different, and preferably have 2 to 13 carbon atoms. A carbamoyl group, a carboxy group, an unsubstituted or substituted alkoxycarbonyl group having preferably 2 to 10 carbon atoms (replacement groups include an A-logen atom and a hydroxy group) , Cyano group, alkoxy group, acyl group, acylamino group, alkylamino group, dialkylamino group, carboxy group, alkoxycarbonyl group, sulfonyl group, sulfonylamino group, sulfo group, aryl group, etc.), no substitution or substitution Aryloxycarbonyl group {substituted by a halogen atom, alkyl group, alkoxy group; nitro group, hydroxy group, carboxy group, cyano group, non-substituted or substituted amino group (substituted by an alkyl group , An acyl group, an alkylsulfonyl group, etc.), an alkoxycarbonyl group, etc. Details, 1-1 2 sulfonyl groups, Surupuamoi Le group number is preferably 1-1 2 carbon atoms, or an electron withdrawing group such as Shiano group.

More specifically, in the formula, X ₂ , X ₃ , and Χ 4 may be the same or different, and represent a hydrogen atom, a halogen atom (e.g., a chlorine atom or a bromo atom), Alkyl groups (eg, methyl, ethyl, propyl, hexyl, etc.), alkoxy groups having 1-6 carbon atoms (eg, methoxy, ethoxy, butoxy, hexyloxy, etc.), hydroxy groups, carboxy groups, carbon atoms Amino groups substituted with an acyl group derived from an alicyclic carboxylic acid or sulfonic acid of Formulas 1 to 6 (for example, acetylamino, hexylcarbonylamino, methanesulfonylamino, ethanesulfonylamino, hexanesulfono Nilamino, 3-sulfopropyl carbonylamino, etc., alkylamino group having 1 to 6 carbon atoms (for example, methylamino, ethyla Roh, A dialkylamino group having a total of 1 to 6 carbon atoms (for example, dimethylamino, getylamino, jib-opening viramino, etc.), a carbamoyl group having 2 to 7 carbon atoms (for example, methylcarbamoyl, ethylcarbamoyl, etc.), A sulfamoyl group having 1 to 6 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, etc.) or an alkoxycarbyl group having 2 to 6 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, pentyloxycarbonyl, etc.) ).

R 1, R 2, R 3 and R 4 may be the same or different, and each represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms (e.g., methyl, ethyl, bromo, butyl, Pentyl, hexyl, octyl, 2-chloroethyl, 3-chloropropyl, 2-bromoethyl, 2-hydroxyxethyl, cyanomethyl, 2-cyanoethyl, 3-cyanoprovir, 2-methoxethyl, 3-methoxyxivir , 2-ethoxyhexyl, 3-ethoxypentyl, 2-isobropoxicetyl, acetylmethyl, 2-acetylethyl, benzoylmethyl, acetyloxymethyl, ethylcarbonylcarbonylmethyl, 2,2,2—trifluoroethylcarbonylcarbonyloxy Methyl, isobutyrylcarbonylcarbonyl, 2- (acetyloxy) ethyl, 2 — (2 , 2, 2 — trifluoroethylcarbonyloxy) ethyl, 2 — (isopropylcarbonyloxy) ethyl, benzoyloxymethyl, 4-chlorobenzoyloxymethyl, 412trobenzo Yloxymethyl, acetylaminoethyl, 2— (ethylcarbonylamino) ethyl, methylcarbamoylmethyl, methylaminoethyl 2-((ethylamino) ethyl, 2- (dimethylamino) ethyl, 2- (ethylamino) ethyl, carboxymethyl, 2-carboxyshetyl, 3-carboxybutyl, 6-carboxyhexyl, methoxycarbonylmethyl , Ethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, isopropyloxycarbonylmethyl, 3- (isopropyloxycarbonyl) butamate, 2 — (methoxycarbonyl) ethyl, 2 — (ethoxycal Bonyl) ethyl, 2- (2,2,2—trifluoroethoxycarbonyl) ethyl, phenoxycarbonylmethyl, methylsulfonylmethyl, ethylsulfonylmethyl, 2— (methylsulfonyl) ethyl, 2 — (Butylsulfonyl) ethyl, methylsulfonylua Nomethyl, 2- (methanesulfonylamino) ethyl, ethanesulfonylaminomethyl, 3— (ethanesulfonylamino) brovir, methylsulfamoylethyl, methylaminocarbonylaminoethyl, 2-sulfoethyl, 3-sulfobrovir, 4- Sulfobutyl, 4-sulfophenylmethyl, phenylmethyl, etc., alkenyl group having 2 to 6 carbon atoms (eg, 3-hexenyl), unsubstituted or substituted phenyl group (eg, phenyl, 4-chlorophenyl, 4-cyano) Phenyl, 4-sulfophenyl, 3-sulfophenyl, 4-hydroxyphenyl, 4-carboxyphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-122 Robundil, etc.) 2 to 7 carbon atoms of the acyl group ( Example, Asechiru, Burobioniru to, Butanoiru, etc. Benzoiru), an alkylsulfonyl group (e.g., main Chirusuruhoni having 1 to 6 carbon Phenylsulfonyl, etc.) or an unsubstituted or substituted phenylsulfuryl group (for example, phenylsulfonyl, 4-chlorophenylsulfonyl, 4-cyanophenylsulfonyl, Sulfophenylsulfonyl, 2-hydroxyphenylsulfonyl, 4-hydroxyphenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylphenylsulfonyl, etc.). Further, in the case of the compounds of the general formulas (W) to (71), Rz may form a 5- to 6-membered ring. The same applies to R ₃ and R 4.

Z! , Z ₂ , Z 3, and Z may be the same or different, and have 2 to 13 carbon atoms (for example, acetyl, propanoyl, hexanoyl, benzoyl, 4-aminobenzyl, and 412trobe). Benzoyl, 4-methylsulfonylaminobenzoyl, 4-ethylsulfonylaminobenzoyl, 4-bromosulfonylaminobenzoyl, 3 — hydroxy-4-methylsulfonylaminobenzoyl, etc.), carbon A carbamoyl group having a number of 2 to 13 (for example, methylcarbamoyl group, ethylcarbamoyl, phenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-1methylsulfoilylcarbamoyl) , 3—Sulfophenylcarbamoyl, 4,1-Provirsulfoyurfenilcarbamoyl, 4B Phenylcarbamoyl, 4-methylsulfonylaminophenylcarbamoyl, etc.), a carboxy group, an unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, broboyl) Xycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 1-methylpropo Xycarbonyl, t-butoxycarbonyl, chloroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 3- (hydroxoxyn-propoxy) carbonyl, cyanoethoxycarbonyl, methoxy Tyloxycarbonyl, acetylethyloxycarbonyl, acetylaminoethyloxycarbonyl, methylaminoethyloxycarbonyl, dimethylaminoethyloxycarbonyl, carboxyethyloxycarbonyl, methoxycarbonylethyloxycarbonyl , Methylsulfonylethyloxycarbonyl, methylsulfonylaminoethyloxycarbonyl, sulfoxycarbonyl, phenylethoxycarbonyl, etc., unsubstituted or substituted phenyloxycarbonyl group (for example, phenyloxycarbonyl) Nyl, 4-chlorophenylcarbonyl, 4-methylphenylcarbonyl, 4-methoxyphenylcarbonyl, 4-nitrophenylcarbonyl, 4-hydroxyphenyloxy Such as carbonyl, 4-carboxyphenyloxycarbonyl, 4-cyanophenyloxycarbonyl, 4-dimethylaminophenylcarbonyl, 4-methoxycarbonyl, phenyloxycarbonyl, etc.), and having 1 carbon atom. To 12 sulfonyl groups (eg, methylsulfonyl, ethylsulfonyl, decylsulfonyl, phenylsulfonyl, etc.), and sulfamoyl groups having 1 to 12 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, brovirsulfamoyl, phenylsulfamoyl) , 4 phenyl sulfamo Etc. Le) represent an electron withdrawing group such as Shiano group. Also, Z i and Z ₂ are linked to form a ring (eg, birazolone II, birazolo triazol ring, (A virazoloimidazole ring, an oxindole ring, an oxyindazoviridine ring, an isoxazolone II, a barbizolic acid II, a dioxytetrahydroviridine ring, an indandione ring, etc.). The same applies to z ₃ and z _4.

 Z 5 and Z 6 may be the same or different. , Dioxytetrahydropyridin 瓖, indandione ring, etc.).

Z 7 and Z β may be the same or different and each have an aryl group having 2 to 13 carbon atoms (e.g., acetyl, brobionyl, hebutanoyl, benzoyl, 4-aminobenzoyl, 412 trobenzoyl, 4 -Methansulfonylaminobenzoyl, 4-ethanesulfonylaminobenzoyl, 4-propanesulfonylaminobenzoyl, 3-hydroxy-41-methanesulfonylaminobenzoyl, etc.), having 2 to 2 carbon atoms 1- 3 carbamoyl groups (eg, methylcarbamoyl group, ethyl carbamoyl, phenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-torophenylcarbamoyl, 4-methylsulfonylphenylcarbamoyl, 3-sulfofenylcarbamoyl , 4-loop mouth bilsulfoyurfenilcarbamoyl, 4-methylsulfonylamino Carbamoyl), a carboxy group, an unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, 1 -Methyl brobo 1 β

Xycarbonyl, t-butoxycarbonyl, chloroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 3-hydroxypropoxycarbonyl, cyanoethoxycarbonyl, methoxyethyloxycarbonyl, acetyl Ethyloxycarbonyl, acetylaminoethyloxycarbonyl, methylaminoethyloxycarbonyl, dimethylaminoethyloxycarbonyl, carboxyethyloxycarbonyl, methoxycarbonylethyloxycarbonyl, methylsulfonyl Tyloxycarbonyl, methanesulfonylaminoethyloxycarbonyl, sulfoethoxycarbonyl, phenylethoxycarbonyl, etc., unsubstituted or substituted phenyloxycarbonyl group (for example, phenyloxycarbonyl, L-phenylcarbonyl, 4-methylphenylcarbonyl, 4-methoxyphenylcarbonyl, 4-nitrophenylcarbonyl, 4-hydroxyphenylcarbonyl, 4-carboxyphenyl Oxycarbonyl, 4-cyanophenyloxycarbonyl, 4-dimethylaminophenyloxycarbonyl, 4-methoxycarbylphenyloxycarbonyl group, etc., and a sulfonyl group having 1 to 12 carbon atoms (eg, methyl Sulfonyl, ethylsulfonyl, decylsulfonyl, phenylsulfonyl, etc.), a sulfamoyl group having 1 to 12 carbon atoms (for example, methylsulfamoyl, ethylsulfamoyl, brovirsulfamoyl, phenylsulfamoyl, 4-sulfone) Phenylsulfamoyl, etc.) Which electron-withdrawing group is represented.

YI and Y ₂ are divalent linking groups and have 1 to 10 carbon atoms 换 or substituted alkylene groups (eg, methylene, ethylene, brovirene, butylene, pentylene, hexylene, heptylene, octylene, xylylene, bromoethylene, etc.), unsubstituted or substituted arylene groups (eg, phenylene group, Naphthylene, chlorophenylene, sulfophenylene, hydroxyphenylene, methoxyphenylene, carboxyphenylene, methylphenylene, nitrophenylene, methanesulfonylaminophene Diene group), carbyl group, and further functional group (for example, oxygen atom, carbonyl group, amino group, carbonyl group, carbonate group, carbonylamino group, ureide group, imido group, sulfonyl group) , Sulfonyloxy group, sulfonylamino group, sulfonyl Alkylene and Ariren groups that have a amino carbonyl group) (e.g.

-(CH ₂ ) ₂ -0- (CH ₂ ) _2- , -CH ₂ C0CH _2- ,

-CH ₂ C0-,-(CH ₂ ) ₂ -0C0- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C0- (CH ₂ ) 2-C00- (CH ₂ ) _2- ,

_{- (CH 2) 2 - 0C0-} (CH 2) 4 -C00- (CH 2) 2 -,

 ,

-(CH ₂ ) ₂ -0C00- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -C0NH- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -NHCONH-(CH ₂ ) _2- ,

-(CH ₂ ) ₂ -C0NHC0- (CH ₂ ) _2- ,

_{- (CH 2) 2 -S0 2} NH- (CH 2) 2 -,

-(CH ₂ ) ₂ NHS0 ₂ NHCONH (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -S0 ₂ NHC0- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ NHS0 ₂ NHC0 ₂ (CH _I ,) 2-,

^C0 ~ ^NHC0NH ~ " ^C °", " ^C0 " ^^ " ^C0 '

_{■ C0- (CH 2) 2 -C0-} , -S0 2 - (CH 2) 4 -S0 2 -,

(CH ₂ ) ₂

-NH (CH ₂ ) ₂ NH—, -N ー, -NHCO (CH ₂ ) ₂ CONH-

_{- NHS0 2 (CH 2) 2} S0 2 NH-, one _{O- (CH 2) 2 - O-} , -CONH (CH 2) 2 NHCO-, one COO (CH _{2) 2} OCO-,

-000-^% — OCO-,-S0 ₂ NH (CH ₂ ) ₂ NHS0 _2- , — S0 ₃ (CO—,

-NHCO

-NHCO--CONH- etc.)

Y a, Y 4 may be the same or different, are 2 stubborn linking group having罨子attractive, such as single CO - Y _s - CO - is like Y ₅ one SO -, one S 0 ₂ · Here, Y ₅ is a 2 钿 fast-linking group, and an unsubstituted or substituted alkylene group having 2 to 10 carbon atoms (for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, xylylene) Such as phenylene), unsubstituted or substituted arylene groups (for example, phenylene group, naphthylene group, cyclophenylene group, sulfofurene group, hydroxyphenylene group, methoxyphenylene group, carboxyphenylene group) , Methylphenylene group, nitrophenylene group, methanesulfonylaminophenylene group, etc.), and further functional groups (for example, oxygen atom, carbonyl group, amino group, carbonyloxy group) Group, a carbonate group, a carbonyl § amino group, Ulei de group, imide group, a sulfonyl group, Suruhoniruokishi group, Suruhonirua amino group, a sulfo Interview Rua amino carbonitrile Interview Le alkylene and Ariren group having a group, etc.) (e.g.

-(CH ₂ ) ₂ -0- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -0C0- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C0- (CH ₂ ) ₂ -C00- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C0- (CH ₂ ) ₄ -C00- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C0-^-C00- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C00- (CH ₂ ) ₂ -,-(CHa) ₂ -C0NH- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -HHC0NH- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -C0NHC0- (CH ₂ ) ₂ --(CH ₂ ) ₂ -S0 ₂ NH- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ HS0 ₂ NHCONH (CH ₂ ) _2- , -(CH ₂ ) ₂ -S0 ₂ NHC0- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHS0 ₂ NHC0 ₂ (CH ₂ ) _2- ,

H-

O-Rudo

Represents

However, in the general formula (melon), the divalent linking group is preferably an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms such as methylene, ethylene, and butylene.

-Ν ⁶ / Ν-, -0-Υ _β -0-, -C0NH-Ye-NHC0-,

-C00-Y _e -0C0-, -S0 ₂ NH-Ye-NHS0 _2- ,

-S0 ₃ -Ye-0S0 _2- . Here Upsilon _beta, Upsilon ₇ is a divalent linking group, no釁换or a substitutable alkylene group having a carbon number of 1 to 0 (e.g., main styrene, ethylene, Burobiren, xenon Ren butylene, pentylene, heptylene , Octylene, xylylene, buguchimoethylene, unsubstituted or substituted arylene groups (for example, phenylene, naphthylene, chlorophenylene, sulfophenylene, hydroxyphenylene, methoxyphenylene) Diene group, carboxyphenylene group, methylphenylene group, nitrophenylene group, methylsulfuraminophenylene group, etc.), carbonyl group, and functional group (for example, oxygen atom, carbonyl group, carbonyloxy group, Carbonate, carbonylamino, ureido, imido, sulfonylamino Alkylene and Ariren group having such sulfonyl § amino group) (e.g.

-(CH ₂ ) ₂ -0- (CH ₂ ) _2- , -CH ₂ C0CHz-.

-GH ₂ C0-,-(CH ₂ ) ₂ -0G0- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C0- (CH ₂ ) ₂ -C00- (CH ₂ ) _2- .

-(CH ₂ ) ₂ -0C0- (CH ₂ ) 4-C00- (CH ₂ ) ₂ - _¾

CH ₂ ) _2- ,

-(CH ₂ ) ₂ -0C00- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -C0NH- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -NHCONH- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -C 0 NHC 0-(CH ₂ ) ₂ --(CH ₂ ) ₂ -S 0 ₂ NH- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ NHS 0 ₂ NHCONH (CH ₂ ) _2- ,

-(CH ₂ ) ₂ -S0 ₂ NHC0- (CH ₂ ) _2- ,

-(CH ₂ ) ₂ NHS0 ₂ NHC0 ₂ (CH ₂ ) _2-

^{"C0-" NHC0NH ~> ~ C0} ", - G0 ^^^" C0 - -C0- (GH 2) 2 -G0-, -S0 2 - represents the _{like) - (CH 2) 4 -S0} 2.

Upsilon _beta is a divalent linking group, an unsubstituted or substitution alkylene group of from 1 to 1 0 carbon atoms (e.g., methylene, ethylene, butylene, etc.), unsubstituted or a substitutable Ariren group (e.g. phenylene group, Represents a hydroxyphenylene group).

 L represents an unsubstituted or substituted methine group (eg, a methyl group or the like as a substituent), and m and n are 0 or 1.

* The arylidene bis-type dyes represented by the general formulas (I) to (71) used in the invention have a diffusive property due to their bis-type structure and can be introduced into the gelatin of photosensitive material as filter dyes. It has immobility and can be fixed at a desired angle. Further, the arylidene bis dye used in the present invention preferably has 2 to 4 sulfo groups or carboxyl groups or a salt thereof (preferably an alkali metal salt or an ammonium salt) in the molecule. this Since sulfo group-containing bis-type dyes are hydrophobic while having appropriate hydrophilicity, they can be made into aqueous solutions or can be dispersed by the so-called “oil-in-ice dispersion method J in ice”, and can be exposed to light by various methods. It can be introduced into the material, and exhibits extremely good coloring properties when processed with a developing solution containing oxalate. This is probably because the bis-type dyes that do not have sulfo groups flow out of the photosensitive material due to the improvement in hydrophilicity that accompanies the formation of new sulfo groups. It is decolored once a nucleophilic group rather than sufficient outflow because hydrophilicity is not sufficiently high, have an unwanted because the neutral dry form蕙occurs a檁色₀

*: In the dyes represented by the general formulas (I) and (Π) used in the present invention, it is preferable that and Z ₂ or Z ₃ and Z ₄ are rapidly linked to form a birazolone ring. The bis-type dye having this structure is excellent in late color.

Further, in the dye represented by formula (I), () or (ΙΠ), when Z ₂ or Z ₃ and z ₄ are a combination of a benzoyl group which may be substituted with a cyano group. Is preferred from the viewpoint of green color during photographic processing.

 The synthesis of the compounds represented by the general formulas (I) to (W) used in the present invention is carried out according to the method described in JP-A-51-36323, etc. And the active methylene compound.

The synthesis of the compound represented by the general formula (I) or (Π) is as follows. It can be obtained by condensing an aldehyde compound represented by the general formula (W) or (匾) with an active methylene (methyl) compound represented by the general formula (K) or (X). General formula (HO

CHO

General formula (Κ)

Z ₁ -CH ₂ -Z ₂

General formula (X)

In addition, enter 1 \ X 2 \ X 3 \ Χ ·, R l, R 2 »

Z ₃ , Z ₄ ,, Y ₂ , m, and n are as described above.

The condensation reaction is advantageously carried out using a solvent having the property of dissolving the starting material, but many reactions proceed without dissolving the starting material. Suitable solvents include alcohols (for example, methanol, , Acetonitrile, ethylene glycol monoalkyl ethers (eg, ethylene glycol monomethyl ether, etc.), amides (eg, acetoamide, dimethylformamide, etc.), ethers (eg, Dioxane), dimethyl sulfoxide, and chloroform. These may be used alone or as a mixture. The reaction is preferably carried out at a temperature ranging from room temperature to the boiling point of the solvent used, but is preferably carried out at 50 to 80 ° C. In order to promote the reaction, it is advantageous to add an acid or base such as viridine, viridine, getylamine, triethylamine, ammonia gas, potassium acetate, ammonium acetate or acetate. The reaction time is usually about 10 minutes to 5 hours.

 The compound represented by the general formula (ΠΙ) can be obtained by condensing an aldehyde compound represented by the following general formula (XI) with an active methylene compound of the general formulas () and (X). General formula

X, where, X 2. R,, R ₂ , R ₃ , R 4, Y i, then m, n is as described above.

 This condensation reaction can be carried out in exactly the same manner as in the case of the compound represented by the general formula (I) or (Π).

 Next, the compounds represented by the general formulas (W) to (VI) are represented by the following general formulas:

The aldehyde compounds represented by (ai) and (a) are converted to the general formula ()

The compound can be obtained by condensing with an active methylene compound represented by formula (XVI). This condensation reaction can be carried out in the same manner under the same conditions as in the case of the compound represented by the general formula (I) or (（) <<

-General formula (ΧΠ)

General formula (¾ ■)

General formula (W)

CH ₂ Z ₅ -Yj-Z _e CH ₂ The general formula (

 ,, ζ

CH ₂ CH ₂

General formula (XW)

 X X X R l, R \ R

_{Z 5, Z 6, Z 7} , Z e, Y i, Y 3, Y 4, L, m, n are as defined above.

 具体 Specific examples of the compounds represented by the general formulas (I) to (（) used in the invention are shown below. However, the scope of * discovery is not limited to this.

(1) represented by the general formula (I) or (II)

 Compound

One

 NC,

 HOOC

 1 1 2

 One three

One four

 CH2COOCH2CF3 CH2COOCH2CF3

CH ₃ S0 ₂ NH

1 1 5

~ ^)

I I I

CO 00

t

6

MM) / 98dr / lOd W9W) / 98 OAV I

 CJ1

/

εε I

81 to

I-19

Uto 22

U25

1

1-31

H34

1-37

0

I-40

1 41

 1-42

1 1 4

1 45

ΝΗ ₂

HC0CH2CH2Ci

1- 48 CH ₃ CH ₃

K0 ₃ SCH ₂ CH ₂ CONH- <0 N N- <0) -CH-CH-CH NHCOCH2CH2SO

CH2CH2 o ,, 0

1- 50

1 51

CH = CH- CH

0 N

-52

, O) -C0NH CH-CH = CHS0 ₃ K 0

N =,

—55

1 56

1- 57

One 58

0

t

6 I

1

1

1 75

Compound represented by formula (m)-1-

-2.

O - Four.

C ₂ H ₅ S0 ₂

CaHsSOz

- Five.

— 6.

~ 9.

Ten.

SO3K 2- 11.

 SO3K-12.

S0 ₃ Na

Dimension

I

— 16.

— 17.

S0 ₃ Na 18.

— 19.

 'ZZ -z

 ^ 9

69P0I9S OAVWKH) / 98dr / lOd

) —Compounds represented by general formulas (17) to (VI)

 I-1 2.

C ₂ H ₅

N

CN

3.

• L -I

• 9

 9

WMK) / 98df / lDd 63

3- 9.

CF ₃ CH ₂

OCH ₂ CF ₃

 1-10.

I 11.

 3- 12.

3- 13.

I 14.

; -15.

3-17.

C H

3- 3

 'ZZ- £

'OS

3-1 23.

 3- 24.

3 to 26.

 3-28.

3-29.

3-30.

I 31.

3- 32.

CH3

 3- 33.

C NHC0

 3- 3.

CH ₂ COOCH (CH ₃ ) ₂ CH ₂ COOCH (CH ₃ ) ₂

 · 9ε

· Ε -ε

Specific methods for synthesizing the typical compounds represented by the general formulas (I) to (VI) used in the present invention are shown below, but other compounds can be synthesized by the same method.

Synthesis Example 1 (Synthesis of Illustrative Compounds 1-1)

 N, N'-bis-cyanoethyl-N, N'-bis- (4-formyl-3-methylfurenyl) -11,2-diaminoethane 7.Og and cyanoacetic acid 3.0 Og was stirred in 200 ml of acetonitrile, 3.0 g of vinegar ammonium was added thereto, and the mixture was heated to reflux. After 3 hours, the obtained crystals were filtered, washed with acetonitrile, and dried. Example compound 11 having an absorption maximum wavelength of ice solution of 392 nm and melting point of 274 to 275 was obtained. 7.2 g of the crystals of 1 were obtained.

Synthesis Example 2 (Synthesis of Exemplified Compounds 1 to 13)

 N, N '1-biscyanoethyl-N, N' 1-bis- (4-formylphenyl) 1-1,2-diamminoethane 16.0 g, 3-ethoxy 1 1 1 (4-sulfophenyl) virazolone sodium salt 26.0 g was stirred in methanol 230 mA, to which was added acetic acid 30 ml, and the mixture was heated to reflux. did. After about 1 hour, the reaction system became homogeneous, and then the reaction proceeded for about 1 hour. When the reaction solution was cooled to room temperature, crystals precipitated, and the crystals were filtered, and methanol was added. Washed and dried. Aqueous solution absorption S Large wavelength: 4222 nm, 32.1 g of Exemplified Compound 113 (crystal having a melting point of 300 or more) was obtained.

Synthesis Example 3 (Synthesis of ^ Compound 1-35)

N, N'-Bisanoethyl-N, N'-bis- (4-formyl-13-methylphenyl) 1-1,2-diaminoethane 8.lg, 3 8 1-ethoxycarbone-l- (3-sulfopropyl) virazolone (9.9 g) was stirred in methanol (150 ml) and triethylamine (5.6 mA) was added. And acetic acid (15 ml), and the mixture was heated under reflux. After about 2.5 hours, dimethylformamide (150 mA) was added to obtain a uniform reaction solution. Subsequently, a solution of 4.0 g of potassium persulfate in methanol was added to precipitate a crystal. Crystals were precipitated. The crystals were filtered, washed with ethanol and dried. Absorption maximum wavelength 4 8 6 _n m of the aqueous solution, (crystalline melting point 1 8 7 X1 (decomposition)) Exemplary Compound 1 one 3 5 was obtained 1 2. 2 _g.

Synthesis Example 4 (Synthesis of Exemplified Compounds 2-7)

 1, 2 — Bis {5 — (N, N-dicyano-ethylamino) 1-2-holmi-lfueno-g-zetan 8.0 g and 3-ethoxy-1-(4-sulfophenyl) virazolo Stir 9.6 g of sodium sodium salt in methanol (20 ml), add 12 ml of acetic acid and heat to reflux for about 2.5 hours. Then, crystals precipitated. The crystals were collected by filtration, washed with methanol, and dried. The maximum absorption wavelength of the aqueous solution was 412 nm, and the compound 2-7 (an orange crystal having a melting point of 270 or more) having an absorption maximum of 12 nm was obtained. lg got.

Synthesis Example 5 (Synthesis of Exemplified Compound 2-12)

1,2-bis- {5— (N-cyanomethyl-N-methylamino) 1-2-formylanilino} ethane 12.0 g and 3—ethoxy 1- (4-sulfophenyl) villa Stir 18.2 g of zolonnatridium salt in 3 OO ml of methanol, add 17 mL of acetic acid and 1 mA of triethylamine, and heat for about 2 hours Refluxed-the reaction solution to Muroton Crystals were precipitated upon cooling. The crystals were collected by filtration, washed with methanol and dried. Absorption maximum wavelength of aqueous solution 452 nm, Exemplified compound 2-12 (red-orange crystal with melting point of 270 or more) 22.3 g obtained Synthesis Example 6 (Synthesis of Display Compound 3-7)

4 1-formyl-methyl- (2-sulfoethyl) aniline sodium salt 7.9 g and 1,4-bis- {1- (4-sulfophenyl) -1 5— Virazolone 1-yl} butane 8. Mix Og in methanol 18 Omil, add vinegar 15 15 ιη £, triethylamine 5 mA and add. The mixture was heated under reflux for 3 hours, and then 150 ml of water was added to the reaction solution. A solution of 3.7 g of sodium acetate in methanol was quickly added to the filtrate, followed by addition of 50 ml of ethanol, and the mixture was allowed to cool to precipitate crystals. The crystals were collected by filtration and washed with ethanol. The crystals were recrystallized from ethanol and water to obtain 10.1 g of Exemplified Compound 3-7 (orange yellow crystals). Melting point 300 ° C or more, input temperature ϊ 490 II m Synthesis Example 7 (Synthesis of Exemplified Compound 3-22)

4-N-methyl-N- (2-sulfonethyl) anilinnatrium salt 6.6 g and 1,2-bis-[{41- (cyanoacetyl) Enylaminocarbonyl] ethane 5. Og was stirred in methanol 30 Omil, and 10 drops of pyridine as a catalyst was added thereto. The mixture was heated under reflux for about 5 hours. After allowing the reaction solution to cool to room temperature, the crystals were collected by filtration, and the crystals were recrystallized from methanol and water to give the exemplified compound.

To H ₂ 0

3 — 2 2 (Orange yellow crystals were obtained for 6.8 s.

4 52 nm When the dyes represented by the general formulas (I) to (VI) are used as filter dyes, anti-irradiation dyes or anti-halation dyes, any effective dyes may be used. Any amount can be used, but it is preferable to use it so that the optical intensity is not in the range of 0. 05 or 3.0. The timing of addition may be any step before coating, coating of dye the amount is usually 0 0 0 1 ~:... is rather to preferred ^{I g / m 2 0 0 0} 1~ 0 5 dyes according to _beta * invention is g / n, the emulsion曆other hydrophilic roller Lee de Can be dispersed in a variety of known ways throughout the 中間 (intermediate layer, protected 曆, anti-halation slaughter, filter 曆, etc.)

 (1) A method of dissolving or dispersing the dyestuff of the present invention directly in a liquid or hydrophilic color slaughter or after dissolving or dispersing in an aqueous coating solution or a solvent, and then preparing an emulsion and a hydrophilic colloid. Method used in the door · Suitable solvent, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methylcellosolve, JP-A-48-9715, US Patent 3,756,83 It can be added to the emulsion in the form of a solution dissolved in a halogenated alcohol described in No. 0, acetone, ice, pyridin, or a mixed solvent thereof, or the like.

(2) A method of dispersing the compound by dissolving the compound in an oil, that is, a solvent substantially insoluble in water and having a boiling point of about 160 and having a high boiling point or higher, to a hydrophilic coide solution. Examples of the high-boiling solvent include alkyl phthalates (dibutyl phthalate, dioctyl phthalate) as described in US Pat. No. 2,322,027. Rate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, trickle phosphate, dioctyl butyl phosphate) G), carboxylic acid esters (eg, tributyl acetyl citrate), Benzoic acid esters (eg benzoyl octyl), alkylamides

(Eg, getyl lauryl amide), fatty twill esters (eg, dibuty-gishethyl succinate, getyl azelate), trimesic acid esters (eg, trimesine chlorinated tributyl), etc. Can be used. In addition, organic solvents having a boiling point of about 30 * 0 to about 150, for example, ethyl acetate, lower argylacetate such as vinegar butyl, ethyl pi-bionate, 2-butyl alcohol, methyl isobutyl butyl ketone, / 3—Ethoxyxyl acetate, methyl acetate solvent acetate—dissolved in water, and a solvent that can be used, for example, alcohols such as methanol and ethanol.

 Here, the use ratio of the dye to the high boiling point solvent is preferably from 10 to 1/10 (weight ratio).

③ * Includes the dyes and other additives of the invention as photographic emulsion 曆 other hydrophilic colloid 曆 filled bolimar latex composition.

Examples of the polymer latex include a polyurethane polymer, a polymer polymerized from a vinyl monomer, and an acrylic acid ester (a suitable vinyl monomer). Methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, glycidyl acrylate, etc.) Acrylic acid esters (such as methyl methacrylate, butyl methacrylate, octyl methacrylate, and glycidyl methacrylate), acryl amide (butyl acryl amide) , Hexyl acrylamide, ct-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl Luster (vinyl acetate , Halogenated vinyl, (vinyl chloride, etc.), halogenated vinylidene (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene , X—replaced styrene (such as <methyl styrene), nuclear substituted styrene (hydroxy styrene, C3 t3 styrene, methyl styrene, etc.), Ethylene, propylene, butylene, butadiene, acrylonitrile and the like can be mentioned. These may be used alone or in combination of two or more kinds, and other vinyl monomers may be used. May be mixed as a minor component. Other vinyl monomers include itaconic acid, acrylic weave, metaacrylic acid, hydro-Q-xylargyl acrylate, hydroglycial argyl methacrylate, and sulfo-argyl alginate. Tallylate, sulfoalkyl methacrylate, styrenesulfonic acid and the like can be mentioned. ] Etc. can be used.

 These filled bolimar latex are disclosed in JP-B-51-39853, JP-A-51-9943, JP-A-53-93943, JP-A-53-1393, and JP-A-54-32. No. 55, No. 54-1 0 7 9 4 No. 1, No. 5-1 3 3 4 6 No. 5, No. 5-19 0 4 3 No., No. 5 6-19 0 4 7 It can be manufactured according to the methods described in JP-A-56-126680 and JP-A-58-149390.

 Here, the use ratio of the dye to the polymer latex is preferably from 10 to 1/10 (weight ratio).

A method in which a hydrophilic polymer having a charge opposite to that of a dye ion coexists as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. The polymer mordant is a polymer having a nitrogen-containing heterocyclic moiety containing a secondary or tertiary amino group, a polymer having a quaternary cation group, and a polymer having a molecular weight of 500 or more. Or more than 100 000,

 For example, vinyl bilidine polymers and vinyl cation cation polymers described in U.S. Pat. Nos. 2,548,564 and the like; U.S. Pat. Nos. 4,124,386 and others Vinyl imidazolium cation polymer which has been used; gelatin and the like which can be crosslinked with gelatin disclosed in U.S. Pat. No. 3,625,694, etc .; U.S. Pat. No. 3,959,9 Aqueous sol-type mordant disclosed in Japanese Patent Application No. 95, JP-A-54-1152228; water disclosed in US Pat. No. 3,898,088 Insoluble mordant; U.S. Pat. No. 4,168,976 Reactive mordant capable of forming a covalent bond with the dye disclosed in the specification and the like; described in British Patent No. 685,475 A polymer derived from an ethylenically unsaturated compound having a dialgylamino argyl ester residue as described above; Products Obtained by Reaction of Polyvinyl Argylketone with Amino Guanidine as described in British Patent No. 850,281; U.S. Pat. Nos. 3,445,23 There can be mentioned, for example, a polymer derived from 2-methyl-2-vinylimidazole as described in No. 1.

方法 Dissolving the compound using a surfactant,

 Useful surfactants may be oligomers or polymers.

For details of this polymer, refer to Japanese Patent Application No. 59-111 (Photo filed on January 26, 1980, filed on Jan. 26, 1979).

 方法 Method of using an ice-philic polymer in place of the high-boiling solvent or in combination with the high-boiling solvent in the above ** For this method, see, for example, US Pat. No. 3,619,195, West Germany It is described in patents 1, 957, 467.

 ⑦ Japanese Patent Application Laid-Open No. 59-113134 / 34 discloses a microforce method using a polymer having a carboxyl group, a sulfonate group, or the like on the side chain.

 During the dispersion of the hydrophilic copolymer obtained above, for example, a lipophilic polymer hydrosol described in JP-B-51-39835 may be added.

 Gelatin is a typical hydrophilic colloid, but any other known hydrophilic colloid that can be used for photography can be used.

 The silver halide emulsion used in the invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Preferred silver halides are silver bromide, chlorobromide, silver bromoiodide or silver bromochloroiodide.

The silver halide particles in the photographic agent layer may have a regular crystal such as a cube or an octahedron, or may have an irregular shape such as a sphere or a plate. It may have an irregular crystal form or a compound form of these crystal forms. It may consist of a mixture of particles of various crystal forms. The silver halide grains may have different phases between the inside and the surface, or may consist of a uniform phase, and grains whose latent image is mainly formed on the surface ( For example, it may be a negative type agent) or may be a particle mainly formed inside the particle (for example, an internal latent image type a agent, a pre-covered direct reversal type agent).

 * The silver halide emulsion used for development has a thickness of 0.5 micron or less, preferably 0.3 micron or less, and a diameter of 0.6 micron or less. Particles with an average asbestos ratio of 5 or more

Tabular grains that occupy 50% or more may be used.Also, monodispersed particles in which particles having an average particle size of soil within 40% occupy 95% or more of the number of particles may be used. An agent may be used.

 The photographic emulsion used in the invention is P. Glafkides, Chimier Physique Pho. togroheque) (Bo Lemon Tele, 1 9

67 years), G.F.Duff in, Photographic Emma j.Region Chemistry (Phtograpic E recommended ulsion)

Che recommend istry (Focal Press, 1966), VL Zelik, et al., Making And * cote Prepared using the method described in Photographic Graphic, Emerging (Making and Coating Photographic Eulsion) (Focal Press, 1964). can do.

When silver halide particles are formed, silver halide solvents such as ammonia, rodane, rhodium ammonium, thioether compounds (for example, US) are used to control the growth of the silver halide grains. Patent No. 3, No. 271, 157, No. 3, 574, 628, No. 3, 704, 130, No. 4, 297, 439, No. 4, 276, 374, etc.), and thione compounds (for example, JP-A-53-144, 193, JP-A-5-82804, JP-A-55-77) No. 737) and amide compounds (for example, Japanese Patent Application Laid-Open No. 54-107717) can be used.

 (C) In the process of silver Q-genide grain formation or physical ripening, potassium salts, zinc salts, thallium salts, iridium salts or their salts, rhodium salts or their complex salts, iron salts or iron complex salts O may coexist

 Silver halide emulsions are usually chemically sensitized. For chemical sensation, see, for example, H. Frieser, D. Grundragen der Fotografischen Prosset · Die G rund 1 gender Photograph isschen Prozesse drawing itSilberhalogeniden The method described on page can be used.

That is, a yellowing method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosalts, thioureas, mercapto compounds, rhodanins); Noble metal compounds (for example, gold complex salts, etc.), stannic salts, amines, hydrazine derivatives, formamidin sulfinic acid, silane compounds) , Pt, Ir, Pd and other metals of the Periodic Table Group can be used alone or in combination. Photo 31 agents used in the invention can contain various compounds for the purpose of preventing capri during the production process, storage or processing of the photosensitive material, or stabilizing the photographic performance. That is, azoles such as benzothiazolyl salts, nitroidazols, triazoles, benzotriazoles, and benzoimidazoles (particularly, nitro- or halogen-substituted); Heterodimercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptothetazoles (especially 1-phenyl-5-) Mercaptotetrazole), mercaptovirimidines; carboxyl group ゃ sulfone group, etc. The above-mentioned α-ring mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinethione; azazane such as tetrazindene (particularly 4-hydroxy-substituted (1, 3, 3a, 7) Add many compounds known as anti-capri agents or stabilizers, such as tetraazaindenes); benzenesulfonate enzymes; benzenesulfinic acid; be able to.

 The silver halide photographic emulsion of the present invention can include a color coupler such as a cyan coupler, a magenta coupler, and a yellow coupler, and a compound dispersing the coupler.

That is, in the color development process, the color is developed by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative). It may contain a compound that can be used. For example, as magenta couplers, 5 — vila zolone power brass, vilazo pi benzimidazole couplers, and cyano acetyl couma lone couplers And yellow-opened acylase nitrile couplers, and yellow couplers include acylacetoamide couplers (for example, penzoylacetoanilides, vivaroylacetoanilides, etc.), and cyan couplers. to naphthoquinone bets Rukapura and Hue Roh is desired arbitrary _β coupler of one-these couplers such Rukapura non-diffusing having a hydrophobic group called roses be sampled groups in the molecule 4 equivalents to Gin'i on Gender or two equivalents. It may be a colored coupler having a color correction effect, or a coupler that releases a development inhibitor during development (a so-called DIR coupler).

 In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound which is colorless and releases a development inhibitor.

 * The photographic emulsions of the invention may be used, for example, for improving sensitivities, increasing contrast, or accelerating development, for example, borial gilenoxide or derivatives thereof such as ethers, esters, and amines, thioether compounds, and thiomorpholine. , Quaternary ammonium chlorides, urethane derivatives, urea derivatives, imidazole derivatives, 3-virazolidones, etc. «

* The halogen halide photographic emulsion of the present invention as a full I filter one dye, at some Iwai La Jeshi ₃ down preventing other various purposes, known water-soluble dyes other than the dyes that will be disclosed in the onset ¾ _Β that may be used in combination with (eg, oxanol dyes; hemi-giosol dyes and merocyanine dyes) or as a spectral sensitizer: *: other than the dyes described in the invention May be used in combination with known cyanine dyes, melocyanin dyes, and hemicyanine dyes. I _β

 写真 Pictures of the invention Various kinds of surfactants are used for various purposes such as coating aids, antistatic, improvement of sperminess, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (for example, acceleration of development, high contrast, sensation). May include ·

 In addition, the light-sensitive material of the invention of the invention relates to anti-fading agents, hardeners, color capri inhibitors, ultraviolet absorbers, protective colors such as gelatin, and various additives. 'Disc closure Vo 1 7 6

(1 9 7 8, XH) R D-Described in 1 7 6 4 3

 Finished emulsions can be used on fine supports such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, and other plastics. Applied on a cupe or glass plate

 * The silver halide photographic light-sensitive material of the present invention includes color bodhi films, color films, color negative films, color reversals (with or without couplers), Photosensitive materials for plate making (for example, lithographic films, lith duplicating films, etc.), photographic materials for cathode ray tube displays (for example, photosensitive materials for emulsion X-ray recording, direct and Materials for indirect photography), photosensitive materials for the tin salt diffusion transfer process), photosensitive materials for the color diffusion transfer process, die-transfer Process

(iibibition transfer process) photosensitive material, emulsion used for silver dye bleaching method, photosensitive material for recording print-out image, photo-developing printing

(Direct Print iiage) Photosensitive materials, photosensitive materials for thermal development, photosensitive materials for physical development, etc. Exposure to obtain a photographic image may be performed using a usual method. That is, natural light (daylight), tungsten light, fluorescent light, mercury lamp, glysen non-arc lamp, carbon arc lamp, xenon lamp Any of a variety of well-known light sources such as a flashlight and a cathode ray tube finsbot can be used. The light emission time is from 1Z100 seconds to 1 second, which is usually used for cameras. of course, 1/1 0 0 0 seconds by Ri short雾光, for example, to 1 1 0 * it is also possible to use the exposure light to 1 1 0 ⁸ seconds using the xenon Roh emissions flash lamp or Kagese'錶管, 1 Exposures longer than seconds can be used. The spectral composition of the light used for exposure can be adjusted as necessary with a color filter. · Laser light can be used for exposure. Excitation by electron beam, X-ray, α-ray, 錶, etc. May be exposed by light emitted from the phosphor

 For photographic processing of photosensitive materials made by using photolithography, see, for example, Research Disclosure No. 176, No. 176, pp. 28-30 (110-176643). As described, any of a known method and a known treatment solution can be applied. Depending on the purpose, this photo processing can be either photo processing that forms a silver image (black and white photo processing) or photo processing that forms a dye image (color photo processing). Good · Processing S degree is usually chosen between 18 and 50, but may be lower than 18 or higher than 50 o

: *: According to the invention, a silver halide photographic photosensitive material having a hydrophilic colloid containing a novel dye which has an appropriate spectral absorption, selectively dyes a specific slaughter, and does not diffuse to other slaughter. Can get the material, According to the Tai invention, a silver halide photographic light-sensitive material having a hydrophilic colloid containing a novel dye which is not colored and does not adversely affect the photographic properties of the photographic agent, particularly the spectral sensitivity, is obtained in photographic processing. Further, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having excellent aging stability. The best mode for carrying out the invention is as follows. The invention will be described in more detail based on a real example. * The performance test method performed in the real example is as follows.

1) Relative sensitivity: the reciprocal of the exposure that gives a density of 1.5 * In the case where no dye is added (samples 1, 19, 60) are each taken as 100;

3.0-0.3

 2) Gradation y =

One (logE X j ― logE ₂ )

 E X,; Exposure dose that gives a capsule density of 0.3

 露 光 露 光; Exposure to give 3.0

3) Capri after irradiation with sailflight: Toshiba anti-fading fluorescent lamp (FLR40SW-DL-X)

(Nu / Μ) Capri at the time of development processing after irradiation for 1 hour under about 200 lux.

4) Remaining color: Absorbance of λ after development processing Dri ai of film after washing

 5) Dyeing and coloring: X 100

Filem D before washing Real trip ΐ¾ 1

 -Five

 A silver halide solution was prepared from silver chlorobromide (5 mol% silver bromide average particle size: 0.25) containing 1 mol equivalent of silver and 10 mol of Rh.

 This emulsion was divided into 9 parts, and 2-hydroxy-14,6-dichloro-1,3,5-triazine sodium as a hardening agent and potassium polystyrenesulfonate as a thickener were added to each emulsion. It was coated on the top so that the coated silver amount was 4 g Znf. As a protective layer, a gelatin solution containing or not containing the dyes shown in Table 1 was coated on these nine emulsion layers so that the amount of gelatin became 1.0 g Zn. As a coating aid for this protective slaughter, sodium P-dodecyl benzenesulfonate was used, and the same thickening agent as in the ¾ layer was used.

 The sample thus obtained was exposed through a light purification process using a P-607 type printer manufactured by Dainippon Screen Co., Ltd., and then developed with a developing solution LD-835 manufactured by Fuji Photo Film Co., Ltd. Konatsu

 Table 1 shows the results.

No.

Note) The test methods for 1), 2), 3) and 4) are as described above. Comparative compounds A, B and C are as follows.

Comparative compound A (described in U.S. Pat. No. 3,002,837)

Comparative compound B

Comparative compound C

NaOOC

As is clear from the results shown in Table 1, in Samples 7 to 9, most of the dye added to the protective layer was diffused into the emulsion, and although safe sailing was obtained, the decrease in y was remarkable. Sample 9 has almost no diffusion to the emulsion slaughter, but has a significant residual color. On the other hand, in the samples 2 to 6 of the wood invention, the dye added to the protective layer did not diffuse into the emulsion layer, and the decrease in y was very small, and the safety of the sailfish was improved. There is almost no residual color.

Example 2

 Exemplified Compound 113 was dispersed and dissolved in 5 g of water and 100 ml of water, mixed with 250 g of a 14% gelatin solution, and stirred using a colloid mill. This composition was applied on a cellulose triacetate film support so as to have an application amount of 8 gZrrf to obtain Sample 10.

 Next, samples were prepared in the same manner using Exemplified Compounds 1—40, 111—11, 115, 117—77 instead of Exemplified Compounds 1—13. And 4. Samples 15 to 17 were prepared in the same manner as above using comparative compounds A, B, D, and E. Further, when an aqueous solution of the compound of the exemplified compounds 1-13 is mixed with a gelatin solution, tricresyl phosphate (dye oil ratio = 1), ethyl acetate and P-dodecylbenzene as an emulsifier are used. Sample 19 was prepared by adding sodium sulfonate and emulsified and dispersed.

 Sample 20 was prepared by dispersing and using the same procedure as in Sample 19 except that polyethylene acrylate (ratio of dye polymer = 1) was used instead of tricresyl phosphate.

Each sample thus obtained was cut to 5 c nf and its visible absorption The spectrum was drenched. Then the sample is 38. C Washed with water (20 m 1) for 3 minutes. After drying the sample, spectrum recharging was performed again, and the dyeing property of the dye was evaluated according to the following equation. D 3 of the film after washing

 Dyeing property = X 1 0 0

 Regarding the color of the film before washing with water, the prepared sample (5cn) was treated with a processing solution of the following composition.

After being soaked at 38 ° C for 3 minutes, washed with ice and dried, it was evaluated by carrying out a vector determination.

 H a O 0 0 0 c c meter 2 S

 Neurodroquinone 5 s Sodium hypochlorite 70 s

 Calcium carbonate 40 s Lithium bromide 2 g Daax,

Decolorization = IX 0 0

Table 2 shows the results obtained for the D-fold ax of the film before Japanese color processing.

2 Table

 (Note) Comparative compounds D and E are as follows Comparative compound D

2s (n)

Comparative compound E (described in US Pat. No. 3,389,994)

CH, NHCOCH,

CH, CH- (0>-NHCOCH,

As is clear from the results in the above table, all of the samples used in the large invention are stable even when washed with water, have sufficient dyeing properties, and have a substantially complete示 す Shows color.

 In addition, as can be seen from the results of Sample 19, (4) the dyestuff of the present invention exhibits excellent dyeing properties and late-coloring properties even when used by emulsification and dispersion.

Real example 3

. Per mol of silver 0 8 X 1 0 (average particle size containing 5 mol% of silver bromide.; 0 2 3) _ ⁵ moles of R h silver chlorobromide containing silver halide emulsion mist consisting of Made.

 This emulsion was divided into 11 parts, and the same compounds as in Example 1 were added as a hardener and a thickener, and the emulsion was coated on a polyethylene terephthalate film so that the silver amount was 3.8 g / nf. . Gelatin (amount to give lgZn), mordant shown below (amount to give 0.05 g Zn), and various dyes shown in Table 3 were dissolved in water and coated as a protective layer on this emulsion. . The same compound as in Example 1 was used as a coating aid.

 Mordant

(C ₂ H5) ₂ H

The sample thus obtained was treated in the same manner as in Example 1, and the relative sensitivity, y, fog after irradiation with the sail plate, and residual color were tested in the same manner as in Example 1. _Β The results are shown in Table 3

number 3

Note) The test methods for 1), 2), 3) and 4) are as described above.

As is evident from the results in Table 3, the use of the dye in combination with the mordant in the wood invention further reduces the dispersion of the dye in the emulsion sacrifice as compared to the dye alone, thereby further preventing the decrease in y. Therefore, the safety of the sailfish can be improved.

Example 4

 The dyes shown in Table 4 were added to a 5% aqueous gelatin solution, and the same hardening agents, thickeners and coating aids as in Example 1 were added, and gelatin was added to the polyethylene terephthalate film. g Zirf, the dye was applied so as to be 0.25 a haze o lZn.

 The sample thus obtained was designated 40. The sample was baked briefly on ice of C for 5 minutes to examine the dyeing properties of the dye.

 Further, the same sample was subjected to development processing in the same manner as in Example 1, and the residual color property was examined.

 Table 4 shows the results.

Table 4

Note) Test methods 4) and 5) are as described above. Comparative compounds F to I are as follows.

Comparative compounds F, G, H and

F to I substituents

Comparative compound ^R ll ^R 12 ^R 13 ^R 14

F -CH ₃ _0C ₂ H ₅ -GHgCHijCN G -CH ₃ -C00C ₂ H ₅ -CH CHCNH -H -NHCONHCH3 -CH ₃ I -CH ₃ -OH-CHC H <i CN

As is clear from the results shown in Table 4, the samples 32 to 57 of the present invention have almost no residual color during processing and have excellent dyeing properties on gelatin.

Real example 5

Silver 1 mole per silver silver halide consisting of silver chlorobromide containing 0.9 x 10- ^s mole Rh (containing 4 mole% silver bromide; average particle size: 0.25) An emulsion was prepared.

 This emulsion was divided into 6 parts, and the same compounds as those in Example 1 were added as a hardener and a thickener, and coated on polyethylene terephthalate so that the silver amount was 4 gZnf.

 As a protective layer, a gelatin solution containing various dyes shown in Table 5 was coated on this emulsion so that the amount of gelatin became 1.0 OgZrrf. The same compounds as in Example 1 were used as the coating aid and thickener for this protective layer.

 The sample thus obtained was subjected to development processing in the same manner as in Example 1.

Table 5 shows the results.

Table 5 Dyeing 2) 3) Sailing

 Sample coating amount Relative sensitivity

(Exemplified compound No.) Dr ⁴⁾ Residual color Fog after irradiation

 62 1 00 6.5 2.00 0.00

 1-63 0.15 g / nf

 63 (Original ¾) 68 5.8 0.22 0.02

 1-66 0.05 g / nf

 1-0 0.10 g / nf

 64 (") 72 5, 6 0.23 0.01

 1-69 0.10 g / nf

 1-1 4 0.1 g / nf

 65 (") 65 5.40 0.2 1 0. 0 1

 1 — A T · U DS / Ul

66 Comparative compound c 0.15 g / rrf 7 14.4 0.22 0.21

67 nB 0.13 g / rri * 69 4.5.0.22 0.01 Note) The test methods for 1), 2), 3) and 4) are as described above.

Compounds B and C were as described in Example 1.

As can be seen from the results in Table 5, Samples 63 to 65 of the present invention showed little diffusion into the emulsion layer and little y reduction and residual color even when two dyes were added to the protective layer. The safety of the sails has been improved.

Real example 6

 On a polyethylene terephthalate film support, a multi-color photosensitive material sample composed of the following slaughter was prepared.

1st slaughter; Halation prevention slaughter

 Gelatin with black colloid silver

2nd layer; middle layer

 Gelatin containing an emulsified dispersion of 2,5-diethyl octyl hydroquinone

No. 3; No. 1 red emulsion

 Silver iodobromide emulsion (silver iodide; 5 mol%) · · ♦ ♦

 Silver coating amount 1.6g / nf

 Sensitizing dye I · ♦ · ♦ Seal in 1 mole of silver

 4.5 X IP

 Sensitizing dye に 対 し て per mole of silver

.5 X It) - ⁴ mol

 Kabbler C 0.4g / nf

 Kabbler C-1 2 0.03g / nf

 Coupler C-1 3 ♦ 0.02g / nf

No. 4; No. 2 red sensitizer

Silver iodobromide emulsion (silver iodide; 6 mol%) Silver coating amount 1.0g / n Sensitizing dye I per mole of silver

3X 10_ ⁴ mol sensitizing dye π per 1 mol of silver

IX 10 ^_ mole coupler C-1 1 ♦ ♦

 Coupler C-one 0.03 g / nf

 Kabbler C-1 2 ♦ ♦ 0.01 g / n

Chapter 5: Intermediate layer

 Same as Tier 2

6th layer; 1st emulsion 曆

 Silver iodobromide emulsion (4 mol% silver iodide) · ♦ ♦ · 鍰 Coating amount 0.9g / n Sensitizing dye に 対 し て Based on silver mole

5x 1 (Γ ⁴ mol sensitizing dye に 対 し て 1 mol silver

2 Χ 10 ^_ mol Kabbler C 1 5 0.4 g / n

 Kabbler C6 6 ♦ 0.15 g / nf

 Kabbler C—3 · ♦ ♦ 0.05g / n

7th layer; 2nd emulsion layer

Silver iodobromide emulsion (6 mol% silver iodide) ♦ · · · silver coating amount l.lg / n sensitizing dye m silver 3X 10 mole

 Sensitizing dye 17 per mole of silver

1.2X 10- ⁴ mol

 Turnip C-7 • 0.01g / rrf

 Coupler C-1 8 • 0.07g / itf

 Coupler C 6 0.02g / irf

No. 8; Yellow Filter

 Gelatin layer containing yellow colloidal silver and 2,5—g-octyl quinone, an emulsified dispersion of quinone, in a gelatin ice solution

 Yellow colloid silver Silver coating amount Q.Q8g / n

9th layer; 1st blue-sensitive emulsion

 Iodobromide emulsion (silver iodide; 4 mol%)

 鈸 Coating amount Q.4g / n

 Sensitizing dye V · ♦ ♦ * 犟 1 mol

 2 10 mol

 Kabbler C-1 9 ♦ 0.9 g / n

 Kabula C-3 0.05g / n

10th layer; 2nd blue-sensitive emulsion

 Silver iodobromide (Joy iodide; 6 mol%)

 Silver coating amount Q.6g / iif

 增 Sensitive dye V · ♦ · · per mole of silver

1 10_ ⁴ mol

Coupler C 9 0.25g / n 1st 1 曆; 1st protection 曆

 UV absorber Gelatin containing emulsified dispersion of UV-1 曆

1st 2nd layer; 2nd protection 曆

 Gelatin slaughtered with polymethyl methacrylate particles (approximately 1.5 in diameter).

 To each layer, in addition to the above composition, a gelatin hardener H-1 and a surfactant were added. The sample prepared as described above was designated as Sample 68.

 In place of the yellow colloid silver from the eighth slaughter of Sample 68, an emulsion prepared in the same manner as that of the display compound 113 was prepared in the same manner as in Example 1, and the amount of the compound 113 applied was reduced. A sample prepared in the same manner as the sample 68 except that the coating was applied at 0.2 g / n was designated as 69. A sample prepared in the same manner using Comparative Compound C was designated as 70. In addition, a sample was prepared in which the yellow colloid silver of the eighth layer of sample 68 was excluded, and this was designated as sample 71.

The compounds used for sample preparation are as follows

NHCONH-CN

C-1 3

CH ₃

 CH3

 C-1 4

OH C-1 5

Ci C-9

H—

_{C¾ = CH- S0 2 - CH 2} - CONH - CH 2

CH ₂ = CH— S0 ₂ 1 CH ₂ 1 CONH 1 CH ₂

UV-

A / A '= 7/3 (weight ratio) Sensitizing dye I

Sensitizing dye π

Sensitizing dye IE

Sensitizing dye IV

Sensitizing dye V

N (C ₂ H _S ) ₃

The obtained samples 68, 69, and 70 were subjected to edge exposure by a conventional method, and were subjected to the following development processing.

 In addition, a processing solution was prepared by removing 41- (N-ethyl-N- / 8-hydroxyshethylamino) -12-methylanilinate from the color developing solution in the following process, and samples 68 to 1 were prepared. In the following, the processes in steps 2 to 6 were carried out to evaluate the dye's colorability.

The difference between the yellow S degrees of Samples 68 to 70 and the yellow S degree of Sample 71 was defined as ΔD ^B «in.

 Table 6 shows the obtained results.

 The development treatment used here was performed at 38 ° C. as described below.

 1. Color development 3 minutes 1 5 transfer

 2. Bleaching 6 minutes 30 seconds

 3.Wash 3 minutes 1 5

 4. Fixed arrival 6 minutes 30 seconds

 5. Rinse 3 minutes 15 seconds

 6. Stable 3 minutes 15 seconds

The composition of the processing solution used in each step is as follows.

Color developer

 Sodium Utrilotriacetate 1. O g

 Sodium nitrite 4.0 s

 Sodium carbonate 30 g

 Potassium bromide 1.4 g

Hydroxylamine nitrate 2.4 g 4-1 (N-ethyl-N-3

 -Hydroxshecilamino

 1 2—Methylaniline salt 4.5 g with water 1 Q. Bleaching solution

 Ammonia bromide 6.0 g ammonia water (28%) 25.0 cc ethylenediamine

 Natrium tetraacetate iron salt 30.0 g Glacial acid 14.0 cc Add water for 1 s. Fixer

 Sodium Tetrapolyphosphate 2.0 g Sodium Sulfate 4.0 g Ammonium Tiodate (70 mg) 7.5 cc Sodium Bisulfite 4.6 g Add water

 Stabilizing liquid

Formalin 8.0 cc Add water and la

Table 6

(Note) Comparative compounds are as described in Example 2.

System Waru Sample 6 9术発is, AD ^B ring in value no problem is dyed cost decolorizing by 0 process. In addition, the degree of fogging is lower than when silver colloid silver is used, and there is less feeling of extinction when yellow colloid silver is used. In Comparative Sample 70, the dyeing property is not sufficient, and the dye spreads to other colors, causing a significant delusion.

 Samples 68 and 69 were left at 35 ° C and 70% RH for 1 month, and the stability over time was examined. It became clear that fog change and sensitivity change were small.

Real example 7

 A color reversal photographic light-sensitive material, Sample 72, was prepared by coating Nos. 1 to 12 in the following order on a cellulose triacetate film support.

No. 1; Prevention of harassment

 Gelatin with black colloid silver

2nd 曆; Intermediate 曆

 Gelatin slaughtering containing an emulsified dispersion of quinone

No. 3; No. 1 red emulsion

 Silver iodobromide (silver iodide; 6 mol%)

 Silver coating amount Q.5g / n

 Kabbler C 1 0 0.4g / nf

4th layer; 2nd red sensitizer

Silver iodobromide (silver iodide: 6 mol%) Silver coating amount 0.8 _g / n

 Kabbler C-1 0 0.9g / n

Fifth slaughter: middle class

 2,5—Gelatin slaughter containing emulsified dispersion of quinone

No. 6; No. 1 green sensitive emulsion

 Silver iodobromide Silver coating amount lg / itf

 Kabbler C 1 1 Q.4g / n

7th slaughter; 2nd emulsion

 Silver iodobromide 1.lg / nf

 Kabbler C 1 1 0.9g / rrf

8th layer; Yellow Filter II

 A gelatin layer containing silver colloid silver and an emulsified dispersion of 2,5-dioctylhydrid quinone in an aqueous gelatin solution

 Yellow colloid silver Silver coating amount Q.Q8g / n

No. 9 曆; First blue-sensitive emulsion layer

 Silver iodobromide Silver coating amount 0.4g / nf

 Kabbler C 1 1 2 0.5g / n

No. 10 曆; Second blue-sensitive emulsion 曆

 Silver iodobromide Silver coating amount 0.8K / n

 Kabbler C 1 2 0.95g / n

1st 1 曆; 1st protection 曆

 Gelatin layer containing emulsified dispersion of UV absorber UV-

1st 2nd; 2nd protection A gelatin emulsion containing fine-grained emulsion (particle size 0.6, 1 mol% silver iodobromide emulsion) and polymethyl methacrylate particles (diameter about 1.5)

 Then, instead of the yellow colloid of the eighth layer of Sample 72, Exemplified Compound 114 was prepared in the same manner as in Example 1. A sample prepared in the same manner as Sample 72 except that SgZnf was applied was designated as 73.

The compounds used for sample preparation are as follows

C-1 10

(t) C _s H _n → V-OC

(t) C ₅ H

C-1 11

 (CsHii

Then, the obtained sample was subjected to edge exposure with white light and then subjected to the following reversal processing. The development processing used here was performed at 38 ° C. as described below.

 1. First development 6 minutes

 2. Rinse for 2 minutes

 3. Reversal 2 minutes

 4. Color development 6 minutes

 5 Adjustment 2 minutes

 6. Bleaching 6 minutes

 7. Fixed arrival 4 minutes

 8. Rinse for 4 minutes

 9. Stable 1 minute

The following composition is used for the treatment liquid.

First developer

 Ice 700 m J2. Sodium tetralobulinate 2 g

Sodium sulfite 20 _g hydroquinone ♦ monosulfo

 30 g

 Sodium carbonate (monohydrate) 3 0 ε

1—Fenir * 4 methyl

 Hydroxymethyl-3 virazo

 Ridon 2 g

2.5 g of potassium bromide Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 mA

 (P H 10) Reversal liquid

 Ice 700 mil nitro Ν * Ν · Ν-Trimethi

 Lenoskinic acid · 6Na salt 3S Stannous chloride (dihydrate) 1s

P-aminophenol 0 • 1 s Sodium glacial oxide 8 S

BF ¾ 5 ml Add 100 ml of water to add color developer

 Water 700 mJl Sodium sodium tetraborate 2s Sodium phosphite 7S Sodium tertiary phosphate (12 hydrate) 36 g Lithium bromide 1S Potassium iodide (0. 90% £ sodium hydroxide 3 s citrazinic acid • 5 s

N—Echiru N— (/ 8

Rufonamidoethyl) 1 3— ― 21 Methyl-41-aminoaniline

 礞 蠓 Salt 1 1 g Ethylenediamine 3 S Add water 100 000 mil Adjustment liquid Ice 700 mil Sodium nitrite 12 g Ethylenediamine

 Sodium (2 ice salt) 8 S thioglycerin 0.4 mils = acid 3 m Add ice 100 000 m J2. Bleaching solution Water 800 g ethylene diamine tetra acid

 Sodium (dihydrate) 2.0 g Ethylenediaminetetraacetic acid

 Iron (m) ammonium

(2 ice salts) 10.0 g Lithium bromide 10.0 s Add water to 1 000 m 5. Fixer water 800 mil Il ammonium thiophosphate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g

 Add water 0 0 0 m Jl

Stabilizing liquid

 Water 80 0 m Ji

 Formalin (37% by weight) 5.0 m Jl

 Fuji Drivewell 5.0 mi

 Add water 0 0 0 m £

 * Sample 73 according to the invention had good dichroism due to the treatment, and the stin of the highlight part was equivalent to that of sample 72.

 In addition, since the fog value of the first development of the emulsion slicing which was in contact was low, the maximum intensity in the inverted image was increased by 22% in yellow and 11% in magenta as compared with the sample 72.

 Therefore, it can be seen that the thickness of the emulsion layer can be further reduced by using the dye of the present invention.

Example 8

A silver halide was prepared from silver chlorobromide (average particle size of 5 mol% of silver bromide: 0.25) containing IX 10 to ⁵ mol of silver per mol of silver.

This solution was divided into 9 parts, and 2 -hydroxy 4,6 -dichloro-1,3,5-sodium triazine as a hardening agent and potassium polystyrenesulfonate as a thickener were added to each, and polyethylene was added. The silver was applied on the terephthalate film so that the amount of silver applied was 4 g / nf. As a protective slaughter on the 9 emulsions, a gelatin solution with or without the dyes shown in Table 7 was used to reduce the amount of gelatin to 1.0 Og nf. \

It was applied as follows. As a coating aid for this protective layer, sodium ド —dodecylbenzenesulfonate is used.

 The sample obtained in this way was passed through a light wedge, exposed with a Dainippon Screen Ρ-607 type printer, and then developed with a Fuji Photo Film Co., Ltd. developing solution LD-835. .

 Table 7 shows the results.

Table 7 Dyeing material λ 颺 ax coating amount (gZnf) 1) 2) 3) Sailing plate 4) Sample relative sensitivity r Remaining color

(Compound No.) (H ₂ 0) fog after being protected曆irradiation

 00 6.3 95 0.00

2 (Invention) 2-6 427η 0.2 0.2 66 5.8 0 0.2 0 0.0

3 (2-7 412η ro 0.20 63 5.60.19.0.0

4 (2-8 486mi 0.224 60 5.3 0 9 0.0

5 (2- 13 422ηι 0.26 5.5 5.5 0.20 0.0

6 (2 4 401 ηRe 0.25 63 5.4 0.20 0.0

7 Comparative compound Β 43 Omi 0.18 78 4.3 0.20 0.0

8 C 4 ΰ o π Recommended 0.19 68 4.2 0.20 0.0

9 A ^ 44ηι 0, 4 74 5.3 0.23 0.05

(Note) Comparative compounds A, B and C are as follows

Comparative compound A

Comparative compound BS (¾Na

 SOa a

Comparative compound C

SO, Na In ¾ et kana from the results of Table 7, Sample 7, 8 is hardly diffused into the emulsion曆dyes were added to the protective layer, Sefurai DOO safety is obtained, but decreased remarkably _β sample 9 of _y, Although there is almost no diffusion into the emulsion layer, there is a problem that the residual color is remarkable. In contrast,: *: In the samples 2 to 6 of the invention, the diffusion of the dye added to the protective layer to the emulsion layer was not observed, and the decrease in y was very small, and the safety of the sailfish was improved. There is almost no residual color.

Real example 9

. Per mol of silver 0 9 X 1 0 - ⁵ mole silver chlorobromide containing R h (. 5 mol% of silver bromide interleaf no average particle size; 0 2 2 μ «) of the silver halide consisting of An emulsion was prepared.

 This emulsion was divided into 7 parts, and the same compounds as in Example 8 were added as a hardening agent and a thickening agent, and the emulsion was coated on a polyethylene terephthalate film so that the amount of silver became 3.8 g Norrf. Gelatin (amount to become lgZn), mordant shown below (amount to 0.5 gZn) and various dyes shown in Table 8 were dissolved in water on this emulsion (2), and coated as a protective layer. As the coating aid, the same compound as in Example 8 was used.

 Mordant

The sample obtained as in Η was processed in the same manner as in Example 1. In the same manner as in Example 1, the relative sensitivity, a, and the capri and residual color after irradiation with the sail were tested.

_Β The results are shown in Table 8

Table 8 Dyeing materials λ aax 1) 2) 3) Sailing plate 4) Sample mordant Relative sensitivity Ύ

Exemplified Compound No. (H ₂ 0) Capri after residual color illumination

 10 00 6.2 0. 00 0.00

11 (Invention 2-6 427ηι 65 5.7 0.20 0.0

12 (2-14 40 1 ηα 63 5.3 0 .1 9 0 .0

13 (2-9 449 ηι 70 5.8 0.26 0.0

14 (2-6 427ηι Yes 63 5.8 0.20 0.0

15 (2-14 40 1 n 顬 Yes 62 5.5 0 8 0.0

16 (2-9 449 ni Yes 70 5.8 0.26 0. 0

As is evident from the results in Table 8, * by using the dye in combination with the mordant in the invention, the diffusion of the dye into the emulsion layer can be further reduced as compared to the dye alone, and the reduction of the color can be further prevented. Safe flight safety can be improved.

Real example 1 0

 The dyes shown in Table 9 were added to a 5% aqueous gelatin solution, and the same hardening agents, thickeners and coating aids as in Example 8 were added, and 3 g of Zn was added to the polyethylene terephthalate film. It was applied so that the dye became 0.25 olZnf.

 The sample thus obtained was designated 40. After passing through water of C for 5 minutes, the dyeing property of the dye was examined.

 In addition, the same sample was subjected to a development process in the same manner as in Example 8, and the residual color was examined.

 Table 9 shows the results.

Table 9 Dyeing material λ aax 4) Sample, ⁵ ) Dyeing degree Remaining color

 1 7 2-1 1 48 1 n 1 1 0 0 0 0 2

1 8 2-1 2 4 5 2 n-fold 1 0 0 0 0 1

1 9 2-2 2 4 9 7 n 蠆 9 9 0 0 0

2 0 2-2 3 44 9 n Recommended 1 0 0 0 0 2

2 1 2-1 0 5 2 8 n Fiber 9 8 0 0 0

2 2 2-1 5 5 1 7 n-fold 1 0 0 0 0 1

2 3 2-1 7 5 9 5 n 1 0 0 0 0 1

2 4 2-2 0 48 6 n Easy 丄 υ υ 0 0 2

2 5 2-1 6 6 0 4 n 1 1 0 0 0 0 2

2 6 2-1 8 6 3 2 n-fold 1 0 0 0-0 2 m i 1 i o 4 丄 fl 醮 1 0 0 U U

2 8 Comparative compound D 4 2 4n 蠆 6 0 • 0 0

2 9 E 4 5 0 n 蠆 3 0 0 0

3 0 "F 5 0 8 n double 5 0 0 0

3 1 "G 4 3 6 n wax 7 0 0 0

3 2 H H 4 6 8 n heavy 0 0 conflict 0 0

(Note) Compound D is as follows.

Specific compounds E, F, G and H are as follows

S0, Na E to H substituents

As is evident from the results in Table 9, the test materials 17 to 27 of the present invention have almost no residual color in the image processing and have excellent dyeing properties to gelatin.

-) 36 Jingjeon 1 1

 Exemplified Compound 2-7 was dispersed and dissolved in 5 g of 100 ml of water, mixed with 250 g of a 14% gelatin solution, and stirred using a colloid mill. This composition was applied on a cellulose triacetate film support so as to have a coating amount of 8 gZn to obtain a sample 100. Next, a sample was prepared in the same manner using Exemplified Compounds 2-9, 2-10, 2-12, 2-14, 2-18, 2-20 instead of Compound 2-7, The samples were designated as 101 to 106, respectively. Samples 107 to 110 were prepared in the same manner as above using the comparison compounds (A), (B), (C) and (D). In addition, when mixing an aqueous solution of Compound 2-7 with a gelatin solution, add tricresyl phosphate (ratio of dye / oil = 1), ethyl acetate, and sodium P-dodecylbenzenesulfonate as an emulsifier. The sample emulsified and dispersed was applied to obtain sample 111. Sample 111 was prepared by dispersing and using the same method as in Sample 111 except that borethyl acrylate (ratio of dye-nopolymer = 1) was used instead of tricresyl phosphate. Each sample thus obtained was cut into 5 cri, and its visible absorption spectrum was measured. The sample is then rinsed at 38 C for 3 minutes.

(20 mi). After drying the sample, the absorption spectrum was determined again, and the dyeing property of the dye was evaluated according to the following equation. D aax of film after washing

 Dyeability: X 100

For the D aax decolorization of the film before washing, prepare the prepared sample (5 crtf) in a treatment solution of the following composition. -

8. After immersion in C for 3 minutes, washing with water, and drying, an absorption spectrum was performed to evaluate. Treatment liquid composition

H ₂ O 0 0 0 cc

 Meter 2 s

Hydroquinone 5 S Sodium sulfite 70 s Calcium carbonate 40 g Potassium bromide 2 g Decolorization Diax ^{N of} film after processing

Decolorization = (1 IX 0 0

 Table 10 shows the results obtained.

1 o table

 Compound No. Dyeability Decolorization Remarks I U KJ Muu 7 / 丄 1 Π U Π U 丄 U

i Π 1 m _ Q 3 丄 ri q o II 丄 1 f l k ー 丄 1 Π j q Q II 丄 li k 丄 1 k 丄 i 0 r Ω r q q n

1 O 4 Coo 1 4 Q 3 7 f n 丄 u o Coo O

 X 1 A Q

 丄 U

丄 1 Π u A o m — m n \ 丄 U t 3 D n

1 Π 7 Ά} Q o Comparative example X 1 Π U i o¾ \ D) f -f Π Π n

1 n Q o o

 Lam)))

1 1 0, No Q 5 9 o Outside

1 1 1 7 1 0 0 9 8

1 1 2 7 1 0 0 9 7

 Comparative compound (B)

 Comparative compound (c)

Comparative compound (D)

CH ^3. CH- NHCOCH,

NHCOCH ₃ As can be seen from the results in Table 10: *: All of the samples according to the invention are stable even when washed with water, have sufficient dyeing properties, and are substantially treated. Shows complete bleaching properties.

 In addition, as can be seen from the results of Samples 11 and 11, even when the dye of the present invention is emulsified and dispersed, excellent dyeing properties and late coloration are exhibited.

Jeongjeon 1 2

 Each layer was formed on a polyethylene terephthalate film support in exactly the same manner as Sample 68 of Example 6, to prepare a multilayer color photosensitive material sample.

 This sample was designated as Sample 120.

 Instead of the yellow colloid No. 8 in Sample 120, a dispersion prepared by preparing Exemplified Compound 2-7 in the same manner as in Example 8 was applied to Compound 2-7 with a coating amount of 0. A sample prepared in the same manner as 120 except that it was applied so as to have a thickness of 2 g Z rrf was designated as 121. A sample similarly prepared using the comparative compound (C) used in Example 11 was designated as 122. In addition, a sample was prepared by removing the yellow colloid silver of the eighth layer of sample 120, and this was designated as sample 123.

 Each of the obtained samples 120, 122, and 122 was subjected to edge exposure by a conventional method, and subjected to the same development processing as in Example 6.

In the same manner as in Example 6, a processing solution was prepared by removing the 4-((N-ethyl-N- / 3)-(hydroxyxethylamino) -12-methylanilinate) from the color developer in the processing step. Samples 120 to 123 were treated, and the treatments in the following steps 2 to 6 were performed to evaluate the decolorizing property of the dye. The difference between the yellowness of each of Samples 120 to 122 and the yellowness of Sample 123 was defined as m D weight in ^B. Table 11 shows the obtained results.

籙 Sensitive milk slaughter 8th slaughter ΔD ^D chisel in

Relative sensitivity Fogging Sample 1 2 0 Comparative example Yellow colloid silver 0 1 0 0 0.08 Sample 1 2 1 Thick invention Exemplified compound 2-7 0 1 08 0.0.05 Sample 1 2 2 Comparative example Comparative compound C) 0

Thick system Waru Sample 1 2 1 invention, △ D ^B orchids in value no problem Chin color dyes by 0 process. Also, the degree of fogging is lower than when silver colloid silver is used. Also, the change in sensitivity of the film with time was smaller than when yellow colloidal silver was used. The comparative sample 122 has insufficient dyeing properties and spreads to other slaughterhouses, causing remarkable destruction.

Example 1 3

 In the same manner as in the case of the magnifying glass 7, the first to 12th layers were applied on a cellulose triacetate film support to prepare a color reversal photographic material, sample 130.

 Then, in place of the yellow colloidal silver in the eighth layer of sample 130, Exemplified Compound 2-12 was prepared, and a dispersion prepared in the same manner as in Example 8 was coated with Compound 2-12. A sample prepared in the same manner as sample 130 except that the amount of the solution was applied to be 0.2 g n was designated as 131.

 The obtained sample was edge-exposed with white light in exactly the same manner as in the case of the real model, and then subjected to a nine-step development process from the first development to the stabilization process.

 Sample 13 relating to the fat invention had good dichroism due to the treatment, and the stin of the highlight portion was equivalent to that of sample 130.

Real ^^ 1 4

. Ag molar equivalent Li 1 1 X 1 0 - ⁵ mole silver chlorobromide containing R h of (. 5 mol% of silver bromide average particle diameter: 0 2 5 it) preparing a silver halide emulsion consisting of did.

This emulsion was divided into 8 parts, each containing 2 -hydroxy as a hardener. -4, 6-Dichroic port-1, 3, 5-Triazine sodium and potassium polystyrenesulfonate as a thickener were added and coated on a polyethylene terephthalate film so that the coated silver amount was 4 gZnf. As a protective layer, a gelatin solution containing or not containing a dye shown in Table 12 was coated on the eight emulsion layers so that the amount of gelatin became 1.0 Og nonf. As a coating aid for this protective slaughter, sodium P-dodecylbenzenesulfonate was used, and as the thickener, the same compound as in Emulsion I was used.

 The thus-obtained sample was exposed through a light wedge with a P-607 type blinter manufactured by Dainippon Screen, and then developed with a developing solution LD-8335 manufactured by Fuji Photo Film Co., Ltd.

 The results are shown in Table 12.

2 Dye λmax coating amount (gZn 1) 2) 3) Safe light 4) Sample relative sensitivity

(Example Compound No.) (H20) ₂ Remaining

 Protective layer Medium Capri after irradiation

 00 6.2 • 97 0. 00

2 (Invention) 3-4 427nai 0 7 65 5.7 0.

3 (〃 3-1 5 428nn 0 8 〃 0. 22

4 (〃3-26 4 12ηα 0 .20 63 5.5 .5 0 8

5 (〃3-29 4 1 /ma〃5.6.0 .1 9

6 (〃 3-3 4 1 1 no 〃 〃 5. 4 0 8

7 Comparative compound A 43 Οηα 0.168 68 4.2.20

8 B 456 nm 0.1 968 40.2 Note) The test methods for 1), 2), 3) and 4) are as described above.

Comparative compounds A and B are as follows.

Comparative compound A

N, 〇 SO Na

 SO ^ Na

Comparative compound B

SO.Na

 As is evident from the results in Table 12, samples 7 and 8 showed that most of the dye added to the protected water diffused into the slaughterhouse, and safe sailing was obtained, but y was significantly reduced. In contrast, Samples 2 to 6 of the invention had the same or higher safety and residual color as Samples 7 and 8, and diffusion of the dye added to the protected slaughter was observed in the emulsion. And the decrease in y is very small.

Example 1 5

. Per mol of silver 1 OX 1 0 - (. Average particle diameter containing 5 mole% of bromide鈸; 0 2 2) ⁵ moles of silver chlorobromide containing R h to prepare a silver halide emulsion comprising .

 This solution was divided into 7 parts, and the same compounds as in Example 14 were added as a hardener and a thickener, and the mixture was applied on a polyethylene terephthalate film so that the silver amount was 3.8 g Zn. Gelatin (amount to 1 g Zirf), mordant shown below (amount to 0.5 g Zn), and various dyes shown in Table 13 were dissolved in water and coated as a protective layer on this emulsion. . As the coating aid, the same compound as in Example 14 was used.

 Mordant

The sample thus obtained was treated in the same manner as in Example 14, and the relative sensitivity was measured in the same manner as in Example 14. Blistering and residual color were tested. The results are shown in Table 13

Table 3 Dyeing materials λ mai 1) 2) 3) Saflight 4) Sample dye coating amount Mordant Relative sensitivity Ύ

Exemplified compound No. (H _? 0) Capri after irradiation

 00 6 .96 0 .0

10 (invention 3-4 427 na 0.17 g / itf 665.6.200.0.0

11 (〃3-25 422nn 0.2 1 g / n 655.4 4 〃

12 (approx. 3-3 4 nn 0 .20 g / m ² 62 5 .3 0 .18 〃

13 (approx. 3-4 427nm 0.17g / n Available 665.8.0.20

14 (〃3-25 422nm 0.2 1 g / nf 〃65 5.7 〃

15 (〃3-341 1 no 0.20 g / nf〃625.6.180.0.0 Note) The test methods for 1), 2), 3) and 4) are the same as those described above.

As is evident from the results in Table 13, the use of the dye in combination with the mordant in the present invention further reduces the diffusion of the dye into the emulsion layer as compared to the dye alone, thereby further preventing the decrease in y. Therefore, the safety of the boat can be improved.

Example 1 6

 The dyes shown in Table 14 were added to a 5% aqueous gelatin solution, and the same hardening agents, thickeners, and coating aids as in Example 14 were added to obtain gelatin on the polyethylene terephthalate film. Coating was performed so that 3 g of Zn and the dye became 0.25 double ol / nf.

 The sample thus obtained was passed through 40 C water for 5 minutes, and the dyeing property of the dye was examined.

 Further, the same sample was subjected to development processing in the same manner as in Example 14 to check the residual color.

 The results are shown in Table 14.

Surface dye λ oaz 4) Sample ⁵ ) Degree of dyeing residual color

 (V. Example 173 shows, 1 Li {—4 ft »N * ^ o". · ノ), "Clino

 1 6 3-1 478 M 1 0 0 0 0 2

1 7 3-2 49 8 n Recommended 1 0 0 0 0 2

1 8 3-5 48 0 n Recommended 9 7 0-0 1

1 9 3-7 49 0 na 9 4 0 • 0 1

2 0 3-1 0 50 2 n 邐 9 5 0-0 1

2 1 3-1 47 0 n 9 9 0 0 2

2 2 3-1 6 5 0 4 n 邐 9 8 0 • 0 2

2 3 3-1 7 6 1 3 n 9 5 0 • 0 1

2 4 3-2 1 57 9 n-ply 1 0 0 0-0 2

2 5 3-22 452 n Recommend 1 0 0 o o 2

2 6 3-3 0 424n earthquake 1 0 0 0 0 2

2 7 Comparative compound c 45 0 n 鬬 0 0 0 0

2 8, _f D 5 08 n 邐 0 0 0 0

2 9 n E 43 6 n Recommended 0 0 0 0

3 0 F 46 8 na 0 0 0 0

3 1, / G 42 4n 0 0 0 0 Note) Test methods 4) and 5) are as described above.

 Comparative compounds C to F are as follows.

Specific compound C-F

 SO ^ Na ratio 鲛 Compound G

Two

Machine £ s ~ H0. N. H. . ½ --- "

 00. NH. 0 N. H. ½. ¾. -1-

H0 i H. 3HNH --- eH. H. ¾. -"

CO

 • — (

cm

 n

 93 O I

UQM b

As is evident from the results in Table 14, Samples 16 to 26 according to the present invention have almost no residual color in the development processing and have excellent dyeing properties to gelatin.

Example 1 7

 Exemplified compound 3-1 was dispersed and dissolved in 5 g of water (100 g), mixed with 250 g of a 14% gelatin solution, and stirred using a colloid mill. This composition was applied on a cellulose triacetate film support so as to give a coating amount of 8 g of i irf to obtain a sample 100.

 Next, samples were prepared in the same manner using Exemplified Compounds 3-3, 3-4, 3-5, 3-7, 3-15, 3-21 instead of Exemplified Compound 3-1. 0 1 to 106 were set. Samples 107 to 110 were prepared in the same manner as described above using comparative compounds (H), (1), (J), and (K). In addition, for example compound 3-4 of sample 102, when the aqueous solution was mixed with the gelatin solution, tricresyl phosphate (dye / oil ratio = 1), ethyl acetate and P-dodecylbenzenesulfonic acid as an emulsifier were used. A sample which was emulsified and dispersed by adding soda was applied to prepare sample 111.

 Sample 111 was prepared by dispersing and using the same method as that of sample 111 using polyethyl acrylate (ratio of dye novolimer = 1) instead of tricresyl phosphate.

Each sample thus obtained was cut into 5 cn, and its visible absorption vector was measured. Then the sample is 38. Washed with C for 3 minutes (20 πι £). After drying the sample, the absorption spectrum was measured again, and the dyeing property of the dye was evaluated according to the following equation. D-ax dyeing property of the film after washing: X100 D 鼉 ax of the film before washing The sample prepared (5 cirf) was immersed in a coating of the following composition for 3 minutes at 38. After washing with water and drying, the absorption spectrum was fixed. Treatment liquid composition

H ₂ O 0 00 cc

 Mettle 2 g

 Hydroquinone 5 s Sodium sulfite 70 s

 40 g of calcium carbonate 2 g of lithium bromide D-weight ax,

Decolorization = 1-1 X 0 0

 Dyed color of the pre-treatment film. The results obtained are shown in Table 15.

Comparative compound H)

Comparative compound (I) *

Comparative compound (D)

Comparative compound (K)

 CH, CH- (0- NHCOCH,

CH ₃

NHCOCH, J 55

 1 5 Table

 Dye (Compound No.) Dyeability Late-coloring Lithium Consideration Sample 100 1 3 1 1 1 00 98 The present invention

1 0 1 3-3 1 0h 98 〃

1 02 3-4 1 00 1 0 0 〃

1 03 3-5 1 00 9 9 〃

1 04 3-7 95 1 0 0 ft

1 05 3-1 5 1 00 98 〃

1 06 3-2 1 1 00 9 6 〃

1 07 (H) 98 9 1 Comparative example

1 08 (I) 7 1 0 0 〃

1 09 (J) 88 2 3

 1 1 0 CK) 95 9 0

 m

1 1 1 3-4 1 00 98

1 1 2 3-4 1 00 97 〃

As is clear from the results in Table 15, all of the samples according to the present invention are stable even when washed with water, have sufficient dyeing properties, and are substantially completely treated by the treatment. It shows good color.

 In addition, as can be seen from the results of Samples 11 and 11, the dyestuff of the present invention shows excellent dyeing and decoloring properties even when used by emulsification and dispersion.

Example 18

 Each layer was formed on a polyethylene terephthalate film support in exactly the same way as Sample 68 of Jeongjeong 6, to prepare a multilayer color photosensitive material sample.

 This sample was designated as Sample 120.

 Instead of the yellow colloid silver in the eighth layer of Sample 120, Dispersion in which Display Compound 3-4 was dispersed in the same manner as in Sample 102 of Example 17 was used to obtain a dispersion of Display Compound 3-4. The sample was made in the same manner as the sample except that the coating amount was 0.2 gZn, and the sample made by haze was set to 121. A sample prepared in the same manner using the comparative compound (J) shown in Example 17 was designated as 122. In addition, a sample was prepared by excluding the eighth silver yellow colloid of sample 120, and this was designated as sample 123.

 The obtained samples 12 0, 12 1, and 12 2 were subjected to development processing in exactly the same manner as in the case of Jin Jing Jin 6 with maggot exposure by a conventional method.

In the same manner as in Example 6, a processing solution was prepared from the color developing solution in the processing step except for removing 41- (N-ethyl-N--8-hydroxyxylamino) -12-methylaniline sulfate. Samples 120 to 123 are processed, and the following processes 2 to 6 are performed to evaluate the dye's colorability. One seven. The difference between the yellow S of each yellow S of the sample 1 23 of the sample 1. 20 to 1 22 △ by D Rin in ^B, shows the results obtained in the first 6 Table.

Table 6 綠 Sensitivity ^ agents 曆 Table 8 8 D "Recommended in

Relative Sensitivity Sample 120 Comparison ^ Yellow Co-Ag Silver 0 100 0.08 Sample 1 2 1 Exemplified Compound of the Present Invention 3-410 0 0.05 Sample 122 Comparison Compound (J) 0 Feeling of destruction

-> 8

Thick invention system Waru Sample 1 2 1, the厶D ^B ain value no problem is晚色dyes by 0 process. Also, the degree of fogging is lower than when silver colloid silver is used. Also, the change in sensitivity of the film with time was smaller than when yellow colloidal silver was used. In Comparative Sample 122, the dyeing properties are not sufficient, and the dye diffuses to other colors, causing remarkable desensitization.

Example 1 9

 In the same manner as in Example 7, 1st to 12th samples were applied on a cellulose triacetate film support to prepare a color reversal photographic photosensitive material and a sample 130.

 Then, in place of the yellow colloid silver in the eighth layer of Sample 130, Exemplified Compound 3-15 was prepared, and a dispersion prepared in the same manner as in Example 17 was used as Compound 3-15. A sample prepared in the same manner as Sample 130 except that the coating amount of was 0.2 gZn was designated as 131. The obtained sample was edge-exposed with white light in exactly the same manner as in Example 7, and then subjected to a nine-step development process from the first development to the stabilization process.

 * Sample 13 1 according to the invention had good decolorization by processing, and the stin of the highlight part was equivalent to that of sample 130.

Claims

 The scope of the claims

• A silver halide photographic light-sensitive material characterized by having at least a combination of compounds represented by the following general formulas (I) to (!? 1).

 General formula (I)

General formula (π)

General formula (ΠΙ)

X 2. 86/04694

 160 General formula (W)

General formula (V)

General formula (Π)

(Wherein X _t , X ₂ , X ₃ , and X ₄ may be the same or different and include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, Represents a rubamoyl group, a sulfamoyl group, or an alkoxycarbonyl group.

, R ₂ , R ₃ , and R 4 may be the same or different, and include a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group. Represents an aryl group, an unsubstituted or substituted aryl group, an acyl group or a sulfonyl group. In the general formulas (ΠΙ) to (^), R 2 or R ₃ or R ₄ forms a 5- or 6-membered ring. You may.

, Z ₂ , Z ₃ and Z 4 may be the same or different and represent an electron-withdrawing group. And and Z ₂ or Z ₃ and Z ⁴ may be connected to form 瓖. Z _S and Z 6 may be the same or different and represent a group of atoms forming 瓖, and z ₇ and Z ₈ may be the same or different and represent an electron-withdrawing group.

Upsilon _iota, Upsilon ₂ represents a divalent linking group, Upsilon _3, Upsilon ^. May be made the same or different, represent a divalent linking group having an electron-withdrawing.

 L represents an unsubstituted or substituted methine group. m and n are 0 or 1. )

2. In the compound represented by the general formula (I), (Π) or (ΠΙ), Z 2, Z 3 and Z may be the same or different, and have 2 to 13 carbon atoms. A rivamoyl group, a carboxyl group having 2 to 13 carbon atoms, an unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an unsubstituted or substituted aryloxycarbonyl group, Is a sulfonyl group having 1 to 12 carbon atoms, an electron-withdrawing group selected from a sulfamoyl group and a cyano group having 1 to 12 carbon atoms, or these electron-withdrawing groups and Z ₂ or Z ₃ Z ₄ is linked to form made the Birazoron瓖, Birazoro triazole瓌, Birazoroimida tetrazole ring, Okishiin doll ring, O carboxymethyl imidazolidine-bi lysine瓖, iso Okisazoron瑷, barbituric acid ring, Jiokishite Torahi Doropiri Gin ring and Lee The claims are 瓖 selected from Danjion 瑗 86/04694 '

 — 162. The silver halide photographic light-sensitive material according to item 1.

 3. In the compound represented by the general formula (17), Z a and Z 6 may be the same or different, and are represented by birazolone ビ, bisazolotriazole 瓖, bisazoloimidazole 瑷, oxindole ring, oxyimidazoviridine 瓖, isoxazolone. 2. The silver halide photographic material according to claim 1, wherein the photographic material is selected from a ring, a barbituric acid ring, a dioxytetrahydroviridine ring, and an indandione ring.

4. In the compound represented by the general formula (V), Z ₇ and Z ₈ may be the same or different, and have 2 to 13 carbon atoms, an acyl group having 2 to 13 carbon atoms, and a carbamoyl group having 2 to 13 carbon atoms. Group, unsubstituted or substituted alkoxycarbonyl group having 2 to 10 carbon atoms, unsubstituted or substituted aryloxycarbonyl group, sulfonyl group having 1 to 12 carbon atoms, 1 carbon atom 2. The silver halide photographic light-sensitive material according to claim 1, which is an electron-withdrawing group selected from the group consisting of a sulfamoyl group and a cyano group.

 5. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by any one of formulas (I) to (Ή) has 2 to 4 sulfo groups or carboxyl groups or a salt thereof in the molecule. material.

6. The compound according to claim 1, wherein z ₂ , or z ₃ and z _{4 of the} compound represented by the general formula (I.), (π) or (m) are linked to form a birazolone ring. , Silver halide photographic material.

7-Z! Of the compound represented by the general formula (I), (Π) or (ΙΠ) _{2. The} silver halide copy according to claim 1, wherein z and z ₂ or z ₃ and z ₄ are a combination of a cyano group and an optionally substituted benzoyl group. True photosensitive material.

 8. The silver halide photographic material according to claim 1, wherein the compound represented by any of the general formulas (I) to (! 7) is coated with 0.01 to 1 gZrrf.

 9. The compound according to claim 2 containing a compound represented by the general formula (I) or (Π) having 2 to 4 sulfo groups or a salt thereof. A photographic processing method that specializes in developing and processing silver sensitized photosensitive materials with a developing solution and a processing solution that mixes with oxygenated clay.